EP1103848B1 - Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film - Google Patents

Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film Download PDF

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Publication number
EP1103848B1
EP1103848B1 EP00203917A EP00203917A EP1103848B1 EP 1103848 B1 EP1103848 B1 EP 1103848B1 EP 00203917 A EP00203917 A EP 00203917A EP 00203917 A EP00203917 A EP 00203917A EP 1103848 B1 EP1103848 B1 EP 1103848B1
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Prior art keywords
substituted
unsubstituted
silver
silver halide
grains
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English (en)
French (fr)
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EP1103848A1 (de
Inventor
Ann Agfa-Gevaert N.V. Verbeeck
Paul Agfa-Gevaert N.V. Callant
Freddy Agfa-Gevaert N.V. Henderickx
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/06—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
    • G03C1/122—Azacyanines
    • 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
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • 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
    • 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
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03511—Bromide content
    • 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
    • G03C2005/168—X-ray material or process
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/03—111 crystal face
    • 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

  • This invention relates to a radiographic light-sensitive silver halide photographic film material having thin tabular ⁇ 111 ⁇ hexagonal grains rich in silver bromide, a combination of two radiographic intensifying luminescent phosphor screens with said film material and a black-and-white diagnostic image forming method after exposure of said screen/film combination with X-rays.
  • the film materials are coated with relatively high amounts of silver, in order to provide a suitable sensitometry even if a low radiation dose is applied to the patient as is always desirable.
  • Use of ⁇ 111 ⁇ tabular silver halide grains permits coating of lower amounts of silver if compared e.g. with grains having a more globular shape as applied before practical application of said tabular grains.
  • Last but not least lowering of coating amounts of silver halide in silver halide photographic materials may not lead to loss in image quality due to increased cross-over percentages measured for double side-coated photographic materials, especially for those spectrally sensitized in the green wavelength range of the visible light spectrum, normally expected to show lower image definition than those spectrally sensitive to radiation in the blue to ultraviolet wavelength range.
  • amounts of spectral sensitizer should be increased which perfectly matches with the requirements as set forth above for tabular grains having a high tabularity.
  • high amounts of spectral sensitizer for such grains is closely related with the need for suitable site-directing action of said sensitizer in order to provide an optimized chemical sensitization without further loss processes.
  • a light-sensitive silver halide photographic film material comprising a transparent support and on one or both sides thereof at least one light-sensitive emulsion layer having spectrally and chemically sensitized tabular silver halide grains rich in silver bromide, further having silver iodide in an amount of less than 3 mole % based on silver, with two flat, parallel, hexagonal ⁇ 111 ⁇ crystal faces, said grains accounting for a total projective surface of said parallel crystal faces in said emulsion of at least 50 %, further having an average aspect ratio of at least 2:1 and a grain thickness of from 0.05 up to 0.15 ⁇ m, wherein said emulsion is obtained by adding, prior to chemical sensitisation, a site-directing compound satisfying general formulae (I.1) or (I.2) as described hereinafter in the detailed description and in the claims in an amount of not less than 1 x 10 -4 mole per mole of silver coated and one or more J-aggrega-ting
  • a radiographic screen/film combination comprising the light-sensitive silver halide photographic film material in combination with a pair of supported or self-supporting X-ray intensifying screens has also been disclosed, wherein said screens essentially consists of luminescent phosphor particles emitting light in the wavelength range for which the film material has been made spectrally sensitive.
  • a black-and-white image-forming method providing diagnostic images comprising the steps of exposing said screen/film material to X-rays passing a subject to be examined, and processing the film material by the steps of developing, fixing, rinsing and drying.
  • each of the substituents R 1 -R 4 independently represents hydrogen, an (unsubstituted or substituted) alkyl, an (unsubstituted or substituted) aryl or an (unsubstituted or substituted) aralkyl; wherein R 1 and R 2 and/or R 3 and R 4 may form a (substituted or unsubstituted) benzoring, which, if substituted, has the same or different substituents as R 1 -R 4 ; wherein R represents an (unsubstituted or substituted) alkyl, an (unsubstituted or substituted) aryl or an (unsubstituted or substituted) aralkyl group; wherein R' represents hydrogen, an (unsubstituted or substituted) al
  • each of R and R' independently represents (CH 2 ) n H or (CH 2 ) n OH, n being an integer having a value from 1 to 4, (CH 2 ) m (SO 3 - ) or (CH 2 ) m O(SO 3 - ), m being an integer having a value from 2 to 4, (CH 2 ) 2 CH(Y)SO 3 - wherein Y represents CH 3 -, -Cl or -OH; (CH 2 ) m N(R)SO 3 - or (CH 2 ) m N(R'SO 3 - (CH 2 ) n (COO - ) or (CH 2 ) n (COOH), (CH 2 ) s SO 2 - (CH 2 ) t H wherein s equals 2 or 3 and t equals 1 or 2; (CH 2 ) x -Phen-W, wherein W represents -COO - or SO 3 - ; Phen represents phenyl which is substituted
  • charge compensating cations are Li + , Na + , K + , HN + Et 3 , wherein Et represents ethyl, whereas preferred charge compensating anions are Cl - , Br - , I - , - OTos, - OMes, CF 3 SO 3 - , wherein - OTos represents tosylate and - OMes represents mesylate.
  • the silver halide photographic film material of the present invention thus comprises a transparent film support having first and second major surfaces coated on one or both sides of the said major surfaces of the support with at least one photosensitive layer overcoated with a protective antistress layer, said photosensitive layer containing in an amount of at least 50 %, preferably at least 70 % and even more preferably at least 90 % of the total projective surface of all grains a light-sensitive emulsion having ⁇ 111 ⁇ tabular grains rich in silver bromide, silver iodide being present in an amount of less than 3 mole % based on silver, with an average grain thickness of from 0.05 ⁇ m up to 0.15 ⁇ m, further having, as an essential feature of the present invention, the site-directing azacyanine compound satisfying the general formulae (I.1) or (I.2) as described herein in a high amount of not less than 1 x 10 -4 mole per mole of silver halide coated, besides one or more J-aggregating spectrally sensitizing dye(s),
  • the ⁇ 111 ⁇ tabular silver halide emulsion grains, present in light-sensitive emulsion layers of materials according to the present invention, are spectrally sensitized in the blue to near ultraviolet wavelength range and/or green wavelength range, preferably prior to chemical sensitisation, depending on the requirements as set forth by medecins examining radiological images as especially sharpness (low cross-over percentage), but also contrast (which should be a "dedicated contrast” depending on the density range wherein image details should be discernable), speed and density range.
  • the duplitized film material comprises in its light-sensitive emulsion layers coated on a subbed support an emulsion having ⁇ 111 ⁇ hexagonal tabular grains rich in silver bromide, further having silver iodide in an amount of less than 3 mole % based on silver,spectrally sensitive to irradiation in the green wavelength range, but treated before adsorption of the J-aggregate forming green sensitizing dye(s) with azacyanine dyes in the high amounts set forth in the statement of the present invention.
  • the radiographic film material according to the present invention thus treated with high amounts of at least 10 -4 mole per mole of silver of the site-directing azacyanine dye(s) according to the general formula (I) becomes spectrally sensitive to irradiation in the green wavelength range between 500 and 555 nm by the further presence of at least one spectrally sensitizing (orthochromatic) dye having a maximum absorption in the wavelength range between 540 and 555 nm and satisifying the general formula (II) wherein
  • the J-aggregating cyanine dye(s) adsorbed at the grain surface of the preferred silver bromoiodide or silver bromochloroiodide ⁇ 111 ⁇ tabular hexagonal grains corresponds to the general formula (II) wherein R 7 is -C 2 H 5 , Z and Z' are both representing an oxygen atom, at least one of R 5 and R 6 represents
  • the J-aggregating cyanine dye corresponds to the general formula (II) wherein R 11 is hydrogen, Z is an nitrogen atom, T represents hydrogen, 5-phenyl, 5-Cl, 5-OCH 3 or 5-CH 3 and wherein T' represents 5,6-(Cl) 2 ; 5-CN-6-Cl; 5-CF 3 -6-Cl; 5-Cl; 5-CN, 5-CF 3 , 5-CHF 2 , 5-SO 2 CH 3 or 5-SO 2 R 12 (R 12 representing a fluoro-subsituted or non-fluoro-substituted alkyl group), 5-COOR 13 and 5-SO 2 -N (R x ) (R y ) or 5-CO-N (R x ) (R y ), wherein R x and R y each independently represents substituted or unsubstited alkyl groups, which may form a ring with the N-atom to which they are attached.
  • each of Z and Z' represents oxygen and each of T and T' represents Cl or, alternatively, T represents Cl and T' represents Phenyl or vice versa and wherein further R 5 and R 6 represent all combinations of the formulae - (CH 2 ) n SO 3 - wherein n equals 2, 3 or 4, - (CH 2 ) 2 -CH(CH 3 )-SO 3 - and - CH 2 -CHY-CH 2 -SO 3 - wherein Y represents -OH or -Cl; and wherein R 5 , corresponding to the formulae given above, is combined with R 6 corresponding to the formulae - (CH 2 ) J H wherein j equals 1, 2, 3 or 4; - CH 2 -Phen-SO 3 - -CH 2 -Phen-COOH - (CH 2 ) k -Phen-COOH wherein k equals 1, 2 or 3. - (CH 2 ) l -COOH, wherein l
  • said J-aggregating spectrally sensitizing dye is a 5,5'-dichloro-3,3'-bis(SO 3 -R)-9-ethyl-benzoxacarbocyanine with R being n-propylene or n-butylene and more particularly anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyloxa-carbocyanine hydroxide.
  • green-light absorbing spectral sensitizers according to the formulae given in JP-A's 06,035,104; 06,035,101; 06,035,102; 62,191,847; 63,249,839; 01,312,536; 03,200,246; US-A 4,777,125 and DE 3,819,241 may be used.
  • the right choice of said sensitizers or combinations thereof is always related with the purpose of obtaining the highest possible photographic speed while reducing dye stain after processing.
  • average grain volumes can be determined from calculations, after measurement for each individual grain of its volume determined after having applied electrochemical reduction techniques, wherein electrical signals thus obtained are related with silver halide grain volumes after total reduction thereof to metallic silver at the cathode of an electrochemical cell.
  • the percentage of the total projective area of all tabular grains with respect to the total projective area of all grains present in the emulsion is calculated from electron microscopic photographs.
  • Average grain diameters and thicknesses of the tabular grains are calculated after determination of individual grain thickness and diameter, calculated as equivalent circular diameter of the hexagonal surface, from shadowed electron microscopic photographs or scanning electron microscopic photographs. From the average ratios of (equivalent circular) diameter to thickness for each individual tabular grain aspect ratios are determined in order to get ability to further calculate the mean aspect ratio of the tabular grains in the emulsion distribution.
  • Such average crystal diameters for the emulsion crystals present in the light-sensitive layer(s) of the materials according to the present invention are between 0.3 and 3.0 ⁇ m, said grains having two flat parallel ⁇ 111 ⁇ crystal faces, accounting for a total projective surface of said parallel crystal faces in said emulsion of at least 50 %, more preferably at least 70 % and even more preferably more than 90 % of the total projective surface area of said grains.
  • said aspect ratio is preferably 5 or more, i.a., from 5:1 up to 50:1 and more preferably from 5:1 up to 20:1.
  • iodide i.a. less than 3 mole % based on silver. More preferably said iodide is present as silver iodide at the grain surface of the tabular grains in order to get an average amount of iodide over the whole grain volume of less than 3 mole % based on silver, preferably less than 1 mole %, even more preferably from 0.05 mole % up to 0.5 mole %, and most preferably in an average amount of from 0.1 mole % up to 0.4 mole %.
  • the duplitized radiographic film material according to the present invention in the most preferred embodiment thus comprises light-sensitive layers at both sides of the film support wherein the thin ⁇ 111 ⁇ tabular silver halide grains rich in silver bromide are containing silver iodide, in limited amounts of from 0.1 mole % up to 0.4 mole %.
  • the ⁇ 111 ⁇ tabular grain population in the light-sensitive emulsion is further preferably homogeneous, i.e., has a variation coeffient of less and 0.40 and more preferably even of from 0.10 up to 0.30, based on the equivalent circular diameters calculated for the individual ⁇ 111 ⁇ tabular grains.
  • ⁇ 111 ⁇ tabular grain emulsions rich in silver bromide can be found in Research Dislosure No. 389057, p. 591-639 (1996), more particularly in Chapter I. A very useful method has been described in EP-A 0 843 208.
  • Said ⁇ 111 ⁇ tabular hexagonal crystals rich in silver bromide are preferably composed of silver bromoiodide or silver bromochloroiodide (with less than 10 mole % of silver chloride, based on silver).
  • Iodide ions present at the surface of al ⁇ 111 ⁇ tabular hexagonal grains are provided in the preparation method by addition of an inorganic iodide salt as potassium iodide.
  • More preferred as providing slower liberation of iodide in the reaction vessel is addition of organic agents releasing iodide ions in order to provide the low silver iodide concentrations, not exceeding 3 mole %, preferably not exceeding 1 mole % and most preferably not exceeding the range from 0.1 mole % up to 0.4 mole % based on silver over het whole grain volume.
  • organic agents releasing iodide ions has been described e.g. in EP-A's 0 561 415, 0 563 701, 0 563 708 and 0 651 284 and in US-A's 5,482,826 and 5,736,312.
  • iodide ions can be released from iodate as has been described in US-A 5,736,312. Release of iodide in the presence of a compound adjusting the rate of iodide release can be applied as described in US-A 5,807,663.
  • addition of iodide to emulsion grains rich in silver bromide is performed by adding fine preformed grains of silver iodide, whether or not including bromide and/or chloride in minor amounts, said grains having a grain diameter of not more than 100 nm, and ,more preferably, not more than 50 nm.
  • Such fine grains are so-called “Lippmann" emulsions.
  • Addition of said fine AgI-Lippmann emulsions to the surface of the silver halide crystals in order to get a global iodide content of less than 1 mole % in the grain may advantageously proceed as disclosed in EP-A 0 475 191, wherein an excellent speed/fog ratio and a high covering power are attained.
  • Preparation of ⁇ 111 ⁇ tabular grain emulsions is performed in the presence of gelatin or colloidal silica sol as a binder providing colloidal stability during all preparation steps.
  • the precipitation of the tabular silver halide crystals according to the present invention is performed in the presence of a protective, hydrophilic colloid, e.g. conventional lime-treated or acid treated gelatin but also oxidized gelatin (see e.g. EP-A 0 843 208) or a synthetic peptiser may be used.
  • a protective, hydrophilic colloid e.g. conventional lime-treated or acid treated gelatin but also oxidized gelatin (see e.g. EP-A 0 843 208) or a synthetic peptiser may be used.
  • the preparation of such modified 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, No. 16, page 30 (1966). Before and during the formation of the silver halide grains it is common practice to establish a gelatin concentration of from about 0.05 % to 5.0 % by weight in the dispersion medium.
  • tabular silver halide grains used in emulsions according to the present invention are precipitated in the absence of gelatin by using colloidal silica sol as a protective colloid in the presence of an onium compound, preferably a phosphonium compound, as has been described in EP-A 0 677 773.
  • silver halide solvents such as ammonia, a thioether compound, thiazolidine-2-thione, tetra-substituted thiourea, potassium or ammonium rhodanide and an amine compound may be present during grain precipitation in order to further adjust the average grain size.
  • the emulsion can be made free from excess of soluble inorganic salts by a conventional washing technique e.g. flocculation by ammonium sulphate or polystyrene sulphonate, followed by one or more washing and redispersion steps.
  • a conventional washing technique e.g. flocculation by ammonium sulphate or polystyrene sulphonate, followed by one or more washing and redispersion steps.
  • Another well-known washing technique is ultrafiltration.
  • extra gelatin is added to the emulsion in order to obtain a gelatin to silver ratio which is optimized with respect to the coating conditions and/or in order to establish the required thickness of the coated emulsion layer.
  • a gelatin to silver halide weight ratio ranging from 0.3 to 1.0 is then obtained.
  • ⁇ 111 ⁇ tabular silver halide emulsion grains present in light-sensitive emulsion layers of materials according to the present invention, are, besides spectrally sensitized, also chemically sensitized, at least with a preferred combination of labile sulphur compounds and gold compounds, more preferably with compounds providing sulphur, selenium or even tellurium and gold.
  • Chemical sensitization methods for ⁇ 111 ⁇ tabular grain emulsions rich in silver bromide can be found in Research Dislosure No. 389057, p. 591-639 (1996), more particularly in Chapter IV.
  • the total amount of coated silver halide in said film material is less than 7 g/m 2 .
  • a total amount of coated silver halide in said film is more preferably in the range of from 3.0 to 6.0 g/m 2 .
  • radiographic film materials coated at only one side (called “single-side” material) of the support can also be provided with light-sensitive emulsion layers having thin hexagonal ⁇ 111 ⁇ tabular grains as set forth hereinbefore.
  • Such materials already have the advantage of a better image definition as incident light generated by luminescent phosphors is coming from only one side of the film support and as there is no cross-over as is the case with duplitized films having transparent film supports, exposed from both sides of said support by a pair of screens emitting light from their respective luminescent phosphors.
  • duplitized film materials of the present invention are thus irradiated by the light emitted imagewise by X-ray intensifying screens, positioned as a sandwich in intimate contact at both sides of the film coated with light-sensitive emulsion layers having the spectrally and chemically sensitized thin hexagonal ⁇ 111 ⁇ tabular grains, after conversion of X-rays passing through the patient.
  • a diagnostic silver image, in conformity with the X-ray image, is obtained after processing of the film material according to the present invention.
  • the X-ray film material comprises a transparent film support, coated on both sides with at least one silver halide emulsion layer, further overcoated with at least one protective antistress layer and, optionally, an afterlayer as disclosed e.g. in EP-A's 0 644 454 and 0 644 456.
  • the protective antistress layer(s) besides the normally added components (see Examples) a mercapto tetrazole compound, preferably a substituted 1-phenyl 5-mercaptotetrazole compound in exceptionally huge amounts of at least 0.5 mmole per mole of coated silver halide, and even up to an amount 10 mmole. It has namely been established that the presence of such compounds in the protective antistress layer(s) further improves image tone in that a "colder" blue-black image is obtained for at least the same and even an increased covering power.
  • a mercapto tetrazole compound preferably a substituted 1-phenyl 5-mercaptotetrazole compound in exceptionally huge amounts of at least 0.5 mmole per mole of coated silver halide, and even up to an amount 10 mmole.
  • said film is thus arranged in a cassette between two X-ray intensifying screens, both of them making contact with the corresponding light-sensitive side(s), thus forming a film/screen system.
  • a radiographic screen/film combination or system comprising a duplitized film material, in contact with or sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that
  • azacyanine dyes according to the general formulae (I.1) and (I.2) should be used in the said high amounts during the preparation of ⁇ 111 ⁇ tabular grain emulsions as the presence of said dyes not only has a site-directing function, but as it also permits further addition of the J-aggregating spectral sensitizers according to the general formula (II) in lower amounts, without loss in speed, thereby providing better decoloration in the processing.
  • J-aggregating spectral sensitizers suitable for spectrally sensitizing emulsions in materials of the present invention have in part been described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons, while other examples have been given in Research Disclosure Item 22534 and in a more recent overview in EP-A 0 757 285, wherefrom dyes forming J-aggregates on the flat surface of the preferred silver bromoiodide or silver bromochloroiodide crystals are particularly useful.
  • a radiographic screen/film combination comprising the light-sensitive silver halide photographic film material as set forth above in combination with a supporting or self-supporting X-ray intensifying screen, characterized in that said supported or self-supporting X-ray intensifying screen essentially consists of luminescent phosphor particles emitting green light irradiation in the wavelength range between 540 and 555 nm.
  • Suitable supersensitizers are, i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A's 2,933,390 and 3,635,721, aromatic organic acid/for-maldehyde condensation products as described e.g. in US-A 3,743,510 as well as cadmium salts and azaindene compounds.
  • At least one non-spectrally sensitizing dye can be added to an emulsion layer or to one or more non-light-sensitive hydrophilic layers such as e.g. an antihalation undercoat layer between a subbing layer, providing good adhesion between the support and adjacent layers, and a light-sensitive emulsion layer.
  • non-light-sensitive hydrophilic layers such as e.g. an antihalation undercoat layer between a subbing layer, providing good adhesion between the support and adjacent layers, and a light-sensitive emulsion layer.
  • the presence of such dye(s) in adapted amounts is not only recommended to adjust the sensitivity of the different emulsion layers and eventually the required contrast, but also in order to reduce scattering of exposure radiation and thus to enhance sharpness.
  • Preferred dyes are those that are removed easily from the photographic material during wet processing in order not to leave any residual color.
  • these dyes are non-diffusible during coating of the hydrophilic layers.
  • these dyes are the dyes that have been described in e.g. US-A's 3,560,214; 3,647,460; 4,288,534; 4,311,787 and 4,857,446.
  • These dyes may be added to the coating solution as a solid particle dispersions of water insoluble dyes having a mean particle diameter of less than 10 ⁇ m, more preferably less than 1 ⁇ m and still more preferably less than 0.1 ⁇ m. Examples of such dyes are disclosed in EP-A's.
  • the silver halide emulsions used in light-sensitive layers of the material according to the present invention may further comprise compounds preventing the formation of a high minimum density or stabilizing the photographic properties during the production or storage of photographic materials or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are i.a.
  • 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
  • fog-inhibiting compounds are those described in Research Disclosure No. 17643 (1978), Chaptre VI. These fog-inhibiting agents or stabilizers can be added to the silver halide emulsion prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
  • the binder of the layers can be forehardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type, e.g. 1,3-vinylsulphonyl-2-propanol or di-(vinylsulphonyl)-methane, vinylsulphonyl-ether compounds, vinylsulphonyl compounds having soluble groups, chromium salts like e.g. chromium acetate and chromium alum, aldehydes as e.g.
  • N-methylol compounds as 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.
  • These hardeners can be used alone or in combination.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-A's 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • the photographic material according to the present invention may further comprise various kinds of surface-active agents in the light-sensitive emulsion layer(s) or in at least one other
  • 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 carboxyl, 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 saponins,
  • Such surface-active agents can be used for various purposes, e.g. as coating aids, as compounds preventing electric charges, as compounds improving film transport in automatic film handling equipment, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving photographic properties such as higher contrast, sensitization and development acceleration.
  • coating aids as compounds preventing electric charges
  • compounds improving film transport in automatic film handling equipment as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion
  • photographic properties such as higher contrast, sensitization and development acceleration.
  • development acceleration may be useful, which can be accomplished with the aid of 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.
  • Especially preferred developing accelerators are recurrent thioether groups containing polyoxyethylenes as described in DE 2,360,878, EP-A's 0 634 688 and 0 674 215.
  • the same or different or a mixture of different developing accelerators may be added to at least one of the hydrophilic layers at the emulsion side. It may be advantageous to partially substitute the hydrophilic colloid binder, preferably gelatin, of the light-sensitive silver halide emulsion layer or of an hydrophilic colloid layer in water-permeable relationship therewith by suitable amounts of dextran or dextran derivatives to improve the covering power of the silver image formed and to provide a higher resistance to abrasion in wet condition.
  • the photographic material of the present invention may further comprise various other additives such as compounds improving the dimensional stability of the photographic material, UV-absorbers, spacing agents, lubricants, plasticizers, antistatic agents, etc.
  • Suitable additives for improving the dimensional stability are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • UV-absorbers are e.g.
  • benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A'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's 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455.
  • the average particle size of spacing agents is comprised between 0.2 and 10 ⁇ m.
  • Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic material, whereas alkali-soluble spacing agents usually are removed 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.
  • acetamide or polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerine.
  • a polymer latex is preferably incorporated into the hydrophilic colloid layer for the purpose of improving the anti-pressure properties, e.g. a homopolymer of acrylic acid alkyl ester or a copolymer thereof with acrylic acid, a copolymer of styrene and butadiene, and a homopolymer or copolymer consisting of monomers having an active methylene group.
  • the photographic material according to the present invention may comprise an antistatic layer to avoid static discharges during coating, processing and other handling of the material.
  • Such antistatic layer may be an outermost coating like the protective layer or an afterlayer or a stratum of one or more antistatic agents or a coating applied directly to the film support or other support and overcoated with a barrier or gelatin layer.
  • Antistatic compounds suitable for use in such layers are e.g. vanadium pentoxide soles, tin oxide soles or conductive polymers such as polyethylene oxides or a polymer latex, or antistatic agents providing permanent electronic conductivity such as polyethylene dioxythiophenes described e.g. in US-A 5,395,472 and EP-A 1 031 875.
  • said film material (made spectrally sensitive - e.g. to green light as in a preferred embodiment - by suitable spectral sensitization of its light-sensitive emulsion grains) is thus arranged in a cassette with X-ray intensifying screen (emitting green light by presence of suitable green-light emitting luminescent phosphors).
  • X-ray intensifying screen emitting green light by presence of suitable green-light emitting luminescent phosphors.
  • said cassette is provided with two X-ray intensifying screens making contact with two X-ray intensifying screens, being the same or different.
  • two intensifying screens it is not excluded to use two identical screens (having same radiation sensitivity), to use two screens emitting the same irradiation but differing in speed, e.g.
  • an intensifying screen sensitive to blue/UV-irradiation and a screen sensitive to green light is not excluded and may be favorable in order to attain desired properties with respect to sensitometry (desired sensitometric curve from the point of diagnostic view) and/or image quality (granularity and/or image definition, particularly sharpness).
  • Specific intensifying screens or conversion screens emitting green (or blue light as in very particular applications with non-symmetric screens and (a)symmetric duplitized films in screen/film combinations for use in the diagnostic image forming method according to the present invention are the commercially available X-ray generating devices providing an exposure to X-rays with a tube voltage from 20 up to 40 kV (as in mammography) and from 70 kV up to 100 kV (as in chest radiography). It is always desired to expose the patient to a low X-ray dose, if possible, so that exposure to low voltage sources is not excluded and even recommended.
  • a preferred luminescent phosphor coated in the X-ray conversion screen used in a film/screen system sensitive to green light is Gd 2 O 2 S:Tb, emitting light in the wavelength range from 540 tot 555 nm.
  • Said phosphor and its use in intensifying screens have been described extensively in patent literature, e.g. in US-A's. 3,872,309; 4,130,429; 4,912,333; 4,925,594; 4,994,355; 5,021,327; 5,107,125 and 5,259,016 and in GB-Patent 1,489,398 and is suitable for use in the context of the film/screen system according to the present invention.
  • a blue/UV emitting screen is used at one side, said screen is provided with blue/UV emitting luminescent phosphor particles emitting at least 50 % and more preferably at least 80 % of their emitted radiation in the wavelength range shorter than 420 nm
  • Typical blue-UV emitting phosphors therein are tantalates as described in PCT-Applications WO 93/1521 and 93/1522, hafnates as described in US-A 5,173,611 and fluorohalides (fluorobromides) of barium and strontium as in WO 91/1357 and US-A 5,629,125, doped with europium and co-doped with samarium as in US-A's 5,422,220 and 5,547,807 and even mixtures of tantalates and fluorohalides as in US-A 5,077,145 and EP-A 0 533 234, replacing CaWO 4 as representative for an older well-known generation of luminescent phosphors.
  • Very useful phosphor particles have e.g.been disclosed in EP-A 0 820 069 wherein particles of niobium doped, monoclinic M, yttriumtantalate phosphor and particles of an europium doped bariumfluorohalide phosphor are composing the screen.
  • Phosphor particles having niobium and gadolinium doped, monoclinic M, yttriumtantalate (MYT) phosphor according to formula YTaO 4 :Gd:Nb are particularly useful.
  • X-ray intensifying screens used in the film/screen system according to the present invention can be self-supporting or supported.
  • X-ray intensifying screens in the screen/film system according to the present invention generally comprise in order: a support (also called substrate), at least one layer comprising phosphor particles dispersed in a suitable binder and a protective coating coated over the phosphor containing layer to protect said layer during use. Further, a primer layer is sometimes provided between the phosphor containing layer and the substrate to closely bond said layer thereto.
  • X-ray intensifying screens in the film/screen system according the present invention can be self-supporting or supported.
  • X-ray intensifying screens generally comprise in order: a support (also called substrate), at least one layer comprising phosphor particles dispersed in a suitable binder and a protective coating coated over the phosphor containing layer to protect said layer during use. Further, a primer layer is sometimes provided between the phosphor containing layer and the substrate to closely bond said layer thereto.
  • a plastic film is preferably employed as the support material.
  • supports characterized by their reflectance properties, expressed as % reflectance over the wavelength range from 350 to 600 nm, are particularly used as described e.g. in US-A 5,381,015.
  • Such supports can be highly light reflecting as e.g. polyethylene terephthalate comprising a white pigment, e.g. BaSO 4 , TiO 2 , etc., or it can be light absorbing supports, e.g. polyethylene terephthalate comprising a black pigment, e.g. carbon black.
  • Supports comprising dyes or pigments that absorb light of a specific wavelength can also be useful in the preparation of X-ray intensifying screens in the film/screen system according to the present invention.
  • the phosphor layers contain sufficient binder to give structural coherence to the layer.
  • a mixture of two or more of these binders may be used, e.g., a mixture of polyethyl acrylate and cellulose acetobutyrate.
  • the weight ratio of phosphor to binder is generally within the range of from 50:50 to 89:11, preferably from 80:20 to 89:11.
  • the screen used in a screen/film system may comprise a supported layer of phosphor particles dispersed in a binding medium comprising one or more rubbery and/or elastomeric polymers as described in EP-A's 0 647 258 and 0 648 254.
  • a ratio by weight of pigment to binding medium of more than 90:10 and more preferably of at least 93:7, e.g. 98:2 can be obtained providing besides an excellent image resolution a high ease of manipulation as a result of a good elasticity of the screen and good adhesion properties between the support and the phosphor layer.
  • a protective layer is generally provided on top of the fluorescent layer.
  • the protective coating has a layer thickness d comprised between 1 and 50 ⁇ m and an embossed surface roughness is applied for high ease of manipulation, thereby avoiding sticking, friction and electrostatic attraction with maintenance of an excellent image resolution.
  • the embossed protective layer can be provided on the phosphor layer in order to protect it against mechanical and chemical damage as described in EP-A's 0 510 753 and 0 510 754. Assemblies providing means for reducing cross-over to less than 10 % for radiation longer than 300 nm in wavelength have been described e.g. in US-A 5,259,016.
  • a black-and-white image-forming method comprising the steps of contacting the film material according to the the present invention between a sandwich of a pair of supported or self-supporting X-ray intensifying screens , wherein said pair of supported or self-supporting X-ray intensifying screens comprises luminescent phosphor particles emitting at least 50 % of their emitted radiation in the wavelength range for which said material has been made spectrally sensitive; exposing the film to X-rays passing a subject to be examined, (said X-rays having an energy of e.g. from 70 to 100 keV while being in contact with the said screens and preferably having a lower energy); and processing the film by the steps of developing, fixing, rinsing and drying.
  • the said processing is preferably performed in an automatic processsing machine. More in detail for processing the film material of the present invention, preferably an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • the processing dry-to-dry within a short processing time of from 30 to 90 seconds and more preferably from 30 seconds to less than 60 seconds of materials coated from low amounts of silver is made possible by the steps of developing said material in a developer (preferably) without hardening agent; fixing said material in a fixer, optionally without hardening agent; rinsing and drying said material.
  • a normally used configuration in the processing apparatus shows the following consecutive tank units corresponding with, as consecutive solutions: developer-fixer-rinse water.
  • developer-fixer-rinse water As consecutive solutions the sequence developer-fixer-fixer-rinse water-rinse water is preferred.
  • One washing step between developing and fixation and one at the end before drying may als be present.
  • a particularly suitable developer solution is the one comprising a reduced amount of sulphite and ascorbic acid which acts as a main developer and antioxidant as well and which is called “low-sludge” developer.
  • Suitable measures taken therefore have recently been described in the EP-Applications Nos. 99201891 and 99201892, both filed simultaneously June 14, 1999.
  • a particularly suitable fixer solution comprises an amount of less than 25 g of potassium sulphite per liter without the presence of acetic acid wherein said fixer has a pH value of at least 4.5, in order to make the fixer solution quasi odorless.
  • black-and-white silver halide material used e.g. in micrography, in aviation photography, in black-and-white cinefilms, in laserfilms or hardcopy films and in graphic or reprographic applications. Even use thereof in color photographic applications may be useful.
  • A1 and B1 were added during 2822 seconds at a linearly increasing rate going from 7.0 up to 21.11 ml/min. for A1 and from 7.06 up to 21.29 ml/min. in order to maintain a constant UAg potential of + 40 mV in the reaction vessel.
  • A1 and B1 were simultaneously added by double-jet addition during 60 seconds at a rate of 10.0 and 10.04 ml/min. respectively whereby the UAg value was held at a constant value of 50 mV while increasing the flow rate up to 46.49 ml/min. and 46.69 ml/min. respectively over a total time period of 81 min. and 5 seconds.
  • the photographic materials according to these examples comprise one emulsion layer and one protective layer.
  • the coating solutions of the emulsion layers were prepared by adding solutions of the compounds indicated in Table 2 to the melted chemically ripened emulsion samples Nos 1-10 while stirring.
  • the coating solution of the protective layer is given in Table 3.
  • the viscosity and surface tension of the coating solutions were optimised according to the requirements of the coating method.
  • the emulsion layer(s) and the protective layer were coated simultaneously on one side of a substrated polyester support having a thickness of 175 ⁇ m by means of conventional coating techniques.
  • the silver coverage of the emulsions was about 5-5.5 g/m 2 , expressed as an equivalent amount of silver nitrate.
  • the starter solution to be added had the following composition: acetic acid 99 % 15.5 ml KBr 16 g demineralized water up to 100 ml
  • the developed photographic strips were fixed in a conventional fixing bath comprising e.g. sodium thiosulfate and potassium metabisulfite, and then rinsed in water and allowed to dry.
  • a conventional fixing bath comprising e.g. sodium thiosulfate and potassium metabisulfite
  • Sensitometric properties of these film strips are given in Table 4, wherein the sensitometric results have been shown in terms of fog F (figures multiplied by a factor of 1000), speed S (figures multiplied with a factor of 100: the lower the figure, the more sensitive is the emulsion; lowering with 30 units is equivalent with a doubling in speed), overall contrast GG (figures multiplied with a factor of 100, the gradation was measured from the characteristic curve over a density range of 1.75 starting from a density value of 0.25 up to 2.00 above fog) and covering power CP, calculated as maximum density per gram of coated silver. Sensitometric data were obtained by developing in a developer having a composition as indicated above during an overall developing time of 12 seconds.
  • Example 2 The same emulsion as in Example 1 was prepared again.
  • Emulsion Nos. 11-14 After washing, gelatin and water were added in order to obtain a silver halide content of 230.5 g/kg, expressed as AgNO 3 , and a gelatin content of 72.6 g/kg.
  • Example 6 Same coatings in amounts equivalent with about 5 g AgNO 3 per sq.m. (see following Table 6) were prepared as in Example 1 and the strips thus obtained were numbered Materials Nos. 11-14. After exposure and processing, just as in Example 1, following results, summarized in Table 6 were obtained.
  • the temperature was increased up to 70°C over a period of 32 minutes: UAg was controlled and should be in the range from 44.5 ⁇ 5 mV (measured versus a Ag/AgCl(sat.) reference electrode. pH was set to a value of 5.0 + 0.3 and immediately thereafter a solution of 50 g of inert gelatin in 500 ml of demineralized water of 70°C was added.
  • Bl was added at a rate of 7 ml/min. during 120 seconds, while simultaneously adding by double jet A1 at a rate of 7.23 ml/min..
  • A1 and B1 were added during 2808 seconds at a linearly increasing rate going from 7.0 up to 21.11 ml/min. for A1 and from 7.23 up to 21.74 ml/min. for B1 in order to maintain a constant UAg potential of + 10 mV in the reaction vessel.
  • A1 and B1 were simultaneously added by double-jet addition during 60 seconds at a rate of 10.0 and 10.14 ml/min. respectively time during which the UAg value was held at a constant value of 30 mV, further increasing the flow rate up to 46.39 ml/min. and 47.04 ml/min. respectively over a total time period of 80 min. and 52 seconds.
  • the cross-over percentage was determined as follows. Double side coated samples were adjusted between a single green light emitting screen (CURIX Ortho Regular, trademarked product from Agfa-Gevaert NV, Mortsel, Belgium) and a white paper replacing the second screen. This film-screen element directed with its light emitting screen to the X-ray tube, was exposed with varying radiation doses, expressed as log E(xposure). After processing the minimum dose needed to obtain a density of 0.5 above fog was determined from the front layer (log E front ) and from the back layer (log E back ) separately. The cross-over percentage was then calculated from the following equation: % C . O .

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Claims (10)

  1. Lichtempfindliches fotografisches Silberhalogenid-Filmmaterial bestehend aus einem lichtdurchlässigen Träger und auf eine oder beide dessen Seiten aufgebracht wenigstens einer lichtempfindlichen Emulsionsschicht mit spektral und chemisch sensibilisierten hexagonalen silberbromidreichen Silberhalogenid-Tafelkörnern, die weiterhin Silberiodid in einer Menge kleiner als 3 mol-%, bezogen auf Silber, aufweisen, mit zwei ebenen parallelen {111}-Kristallflächen, wobei diese Körner wenigstens 50 % einer gesamten projizierten Fläche der parallelen Kristallflächen in der Emulsion ausmachen, weiterhin mit einem mittleren Aspektverhältnis von wenigstens 2:1 und einer Korndicke von 0,05 bis 0,15 µm, wobei die Emulsion erhalten wird, indem vor der chemischen Sensibilisierung eine den allgemeinen Formeln (I.1) oder (I.2) entsprechende Richtung weisende Steuermittel-Verbindung in einer Menge nicht kleiner als 1 x 10-4 mol pro mol aufgetragenes Silber und ein zur Bildung von J-Aggregaten befähigter spektral sensibilisierender Farbstoff bzw. mehrere zur Bildung von J-Aggregaten befähigte spektral sensibilisierende Farbstoffe zugesetzt wird bzw. werden, wobei das Molverhältnis zwischen der Richtung weisenden Steuermittel-Verbindung und dem bzw. den zur Bildung von J-Aggregaten befähigten spektral sensibilisierenden Farbstoff(en) bei einem Korndeckvermögen der hexagonalen {111}-Tafelkörner größer als 50 % wenigstens 1:6 beträgt und wobei die Richtung weisenden Steuermittel-Verbindungen den Formeln I.1 oder I.2 entsprechen
    Figure imgb0027
    Figure imgb0028
     in denen :
    die Substituenten R1-R4 je unabhängig voneinander ein Wasserstoffatom, eine (substituierte oder nicht substituierte) Alkylgruppe, eine (substituierte oder nicht substituierte) Arylgruppe oder eine (substituierte oder nicht substituierte) Aralkylgruppe bedeuten;
    R1 und R2 und/oder R3 und R4 einen (substituierten oder nicht substituierten) Benzolring bilden können, der, wenn er substituiert ist, die gleiche Substituenten wie oder andere Substituenten als R1-R4 aufweist;
    R eine (substituierte oder nicht substituierte) Alkylgruppe, eine (substituierte oder nicht substituierte) Arylgruppe oder eine (substituierte oder nicht substituierte) Aralkylgruppe bedeutet;
    R' ein Wasserstoffatom, eine (substituierte oder nicht substituierte) Alkylgruppe, eine (substituierte oder nicht substituierte) Arylgruppe oder eine (substituierte oder nicht substituierte) Aralkylgruppe bedeutet;
    und wobei Kationen oder Anionen als Gegenionen enthalten sind.
  2. Material nach Anspruch 1, dadurch gekennzeichnet, dass das Molverhältnis zwischen der Richtung weisenden Steuermittel-Verbindung und dem bzw. den zur Bildung von J-Aggregaten befähigten spektral sensibilisierenden Farbstoff(en) 1:3 bis 1:1 beträgt.
  3. Material nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in der Formel (I.1) oder (I.2) R und R' je unabhängig voneinander
    (CH2)nH oder (CH2)nOH, wobei n eine ganze Zahl von 1 bis 4 ist;
    (CH2)m(SO3 -) oder (CH2)mO(SO3 -), wobei m eine ganze Zahl von 2 bis 4 ist;
    (CH2)2CH(Y)SO3 -, wobei Y CH3-, -Cl oder -OH bedeutet;
    (CH2)mN(R)SO3 - oder (CH2)mN (R')SO3 -;
    (CH2)n(COO-) oder (CH2)n(COOH);
    (CH2)sSO2 -(CH2)tH, wobei s gleich 2 oder 3 und t gleich 1 oder 2 ist; (CH2)x-Phen-W, wobei W -COO- oder SO3 - bedeutet; Phen eine gegebenenfalls substituierte Phenylgruppe bedeutet, und x gleich 1, 2, 3 oder 4 ist;
    (CH2)nCONHSO2R oder (CH2)nCONHSO2R' , vorausgesetzt, dass R' ein Wasserstoffatom bedeuten kann; oder
    (CH2)m-(C=O)-O-CH2-(C=O)-CH3, wobei m' eine ganze Zahl von 1 bis 5 ist,
    bedeuten.
  4. Material nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Silberhalogenid-{111}-Tafelkörner ein Aspektverhältnis von wenigstens 5:1, einen mittleren Kristalldurchmesser zwischen 0,3 µm und 3,0 µm und eine mittlere Dicke kleiner als 0,30 µm aufweisen, wobei sie wenigstens 50 % der gesamten projizierten Fläche der Körner ausmachen.
  5. Material nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die silberbromidreichen Körner Iodid in einer Menge von 0,1 mol-% bis 0,4 mol-% aufweisen.
  6. Material nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Silberhalogenid-Körner durch das Vorhandensein eines zur Bildung von J-Aggregaten befähigten spektral sensibilisierenden Cyaninfarbstoffes, der der nachstehenden allgemeinen Formel (II) entspricht, für Strahlung im Wellenlängenbereich von 540 bis 555 nm empfindlich sind
    Figure imgb0029
     in der bedeuten
    Z und Z' unabhängig voneinander je ein Stickstoffatom oder ein Sauerstoffatom und wobei Z mit R8 substituiert ist, wenn Z ein Stickstoffatom ist, und Z' mit R9 substituiert ist, wenn Z' ein Stickstoffatom ist;
    R5, R6 und R8 und R9 unabhängig voneinander je eine substituierte oder nicht substituierte Alkylgruppe,
    R7 ein Wasserstoffatom, eine substituierte oder nicht substituierte Alkylgruppe oder eine substituierte oder nicht substituierte Arylgruppe,
    T und T' unabhängig voneinander je ein Wasserstoffatom, eine substituierte oder nicht substituierte Alkylgruppe, eine substituierte oder nicht substituierte Arylgruppe oder eine substituierte oder nicht substituierte heterocyclische Gruppe;
    (X-)p ein negativ geladenes Atom oder eine negativ geladene Gruppe von Atomen zum Ausgleich der am Farbstoff vorliegenden positiven Ladung(en), und
    (M+)q ein positiv geladenes Atom oder eine positiv geladene Gruppe von Atomen zum Ausgleich der am Farbstoff vorliegenden negativen Ladung(en), wobei p und q je eine ganze Zahl bedeuten, die es ermöglicht, eine elektronisch neutrale Verbindung zu erhalten.
  7. Material nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die als äquivalente Menge Silbernitrat ausgedrückte Gesamtmenge an aufgetragenem Silberhalogenid im Film im Bereich von 3,0 bis 6,0 g/m2 liegt.
  8. Röntgenfilm-Folien-Kombination, die das lichtempfindliche fotografische Silberhalogenid-Filmmaterial nach einem der Ansprüche 1 bis 7 umfasst, in Kombination mit einer trägergestützten oder selbsttragenden Röntgenverstärkerfolie, dadurch gekennzeichnet, dass die trägergestützte oder selbsttragende Röntgenverstärkerfolie im Wesentlichen aus Leuchtstoffteilchen, die grüne Lichtstrahlen im Wellenlängenbereich von 540 bis 555 nm ausstrahlen, besteht.
  9. Röntgenfilm-Folien-Kombination nach Anspruch 8, dadurch gekennzeichnet, dass es sich beim Leuchtstoff um Gd2O2S:Tb handelt.
  10. Schwarzweiß-Bilderzeugungsverfahren mit den Schritten
    - Anordnen des Filmmaterials nach einem der Ansprüche 1 bis 6 in Berührung mit und zwischen einem Paar von trägergestützten oder selbsttragenden Röntgenverstärkerfolien, wobei das Paar von trägergestützten oder selbsttragenden Röntgenverstärkerfolien Leuchtstoffteilchen enthält, die wenigstens 50 % ihrer ausgestrahlten Strahlung im Wellenlängenbereich, für den das Material spektral empfindlich gemacht ist, ausstrahlen;
    - Belichten des Filmmaterials mit von einem zu untersuchenden Objekt durchgelassenen Röntgenstrahlen, wobei die Röntgenstrahlen eine Energie von 70 bis 100 keV aufweisen, während sich das Filmmaterial mit den Folien in Berührung befindet;
    - Verarbeiten des Filmmaterials durch die Schritten Entwickeln, Fixieren, Spülen und Trocknen.
EP00203917A 1999-11-26 2000-11-07 Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film Expired - Lifetime EP1103848B1 (de)

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EP00203917A EP1103848B1 (de) 1999-11-26 2000-11-07 Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film

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EP99204009 1999-11-26
EP99204009 1999-11-26
EP00203917A EP1103848B1 (de) 1999-11-26 2000-11-07 Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film

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US6794105B2 (en) * 2002-11-19 2004-09-21 Eastman Kodak Company Radiographic silver halide film for mammography 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
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
CN104232075B (zh) * 2014-09-30 2016-04-13 郑州大学 一种热致变色荧光温度计材料及其制备方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP1045283A1 (de) * 1999-04-16 2000-10-18 Agfa-Gevaert N.V. Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film

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IT1217814B (it) * 1988-06-09 1990-03-30 Minnesota Mining & Mfg Elementi sensibili alla luce per uso radiografico e procedimento per la formazione di un,immagine radiografica
JPH10197979A (ja) * 1997-01-14 1998-07-31 Fuji Photo Film Co Ltd ハロゲン化銀感光材料
EP0890873B1 (de) * 1997-07-11 2003-10-15 Agfa-Gevaert Kombination von radiographischen UV/blau Verstärkerschirm und Film
EP0953867B1 (de) * 1998-04-29 2004-08-04 Agfa-Gevaert Verfahren zur spektralen Sensibilisierung von tafelförmigen Silberhalogenidkörnern

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Publication number Priority date Publication date Assignee Title
EP1045283A1 (de) * 1999-04-16 2000-10-18 Agfa-Gevaert N.V. Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film

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