EP0276566A1 - Radiographisches Element mit reduziertem Zwischenbildeffekt - Google Patents

Radiographisches Element mit reduziertem Zwischenbildeffekt Download PDF

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Publication number
EP0276566A1
EP0276566A1 EP87311289A EP87311289A EP0276566A1 EP 0276566 A1 EP0276566 A1 EP 0276566A1 EP 87311289 A EP87311289 A EP 87311289A EP 87311289 A EP87311289 A EP 87311289A EP 0276566 A1 EP0276566 A1 EP 0276566A1
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EP
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Prior art keywords
dye
radiographic element
further characterized
element according
radiographic
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EP87311289A
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English (en)
French (fr)
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EP0276566B1 (de
Inventor
Donald Richard Eastman Kodak Company Diehl
Ronda Ellen Eastman Kodak Company Factor
Robert Edward Eastman Kodak Company Dickerson
James Edward Eastman Kodak Company Kelly
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US07/073,256 external-priority patent/US4803150A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • 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
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
    • G03C2001/7448—Dispersion
    • 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
    • G03C2200/44—Details pH value
    • 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
    • G03C2200/46—Details pKa value

Definitions

  • the invention relates to radiography. More specifically, the invention relates to double coated silver halide radiographic elements of the type employed in combination with intensifying screens.
  • While silver halide photographic elements are capable of directly recording X ray exposures, they are more responsive to light within the visible spectrum. It has become an established practice to construct Duplitized® (double coated) radiographic elements in which silver halide emulsion layers are coated on opposite sides of a film support and to sandwich the radiograph element between intensify­ing screen pairs during imaging.
  • the intensifying screens contain phosphors that absorb X radiation and emit light. This light is transmitted to the silver halide emulsion layer on the adjacent face of the film support. The result is that diagnostic radio­graphic imaging is achieved at significantly reduced X-ray exposure levels.
  • a radiographic element of the type described element is character­ized in that the dye is, prior to processing, in the form of microcrystalline particles present in a con­centration sufficient to reduce crossover to less than 10 percent and is capable of being substantially decolorized in less than 90 seconds during processing.
  • the present invention offers significant and unexpected advantages over the prior state of the art. Crossover is reduced below levels heretofore successfully achieved in the art and without desensi­tization of latent image forming silver halide grains.
  • the extremely low crossover levels realized have been made possible by discovering that dyes incorporated in a radiographic element in the form microcrystalline particles can be nevertheless satis­factorily decolorized during the very short process­ing interval conventionally employed in preparing radiographic images.
  • By employing the crossover reducing dyes in microcrystalline form migration of the dyes to latent image forming silver halide grains surfaces and resulting desensitization of these grains is obviated.
  • the present invention permits simpler radiographic element construction than is possible with radiographic elements employing a nonimaging silver halide grains to provide dye adsorption surfaces. Still further, the microcrys­talline form of the dyes allows superior spectral adsorption profiles to be realized as compared to the same or chromophorically similar dyes adsorbed to silver halide grain surfaces.
  • crossover reduction advantages of the present invention are fully compatible with both the crossover reduction and other known advan­tages of high aspect ratio and thin, intermediate aspect ratio tabular grain silver halide emulsions.
  • a radiographic element 100 is positioned between a pair of light emitting intensifying screens 201 and 202.
  • the radiographic element support is comprised of a radiographic sup­port element 101, typically transparent or blue tinted, capable of transmitting at least a portion of the light to which it is exposed and optional, simi­larly transmissive subbing layer units 103 and 105, each of which can be formed of one or more adhesion promoting layers.
  • On the first and second opposed major faces 107 and 109 of the support formed by the subbing layer units are crossover reducing hydro­philic colloid layers 111 and 113, respectively.
  • each of the emulsion layer units is formed of one or more hydrophilic colloid layers including at least one silver halide emulsion layer.
  • Overlying the emulsion layer units 115 and 117 are optional protective overcoat layers 119 and 121, respec­tively. All of the protective layers and hydrophilic colloid layers are permeable to processing solutions.
  • the assembly is imagewise exposed to X radiation.
  • the X radiation is principally absorbed by the intensifying screens 201 and 202, which promptly emit light as a direct function of X ray exposure.
  • the intensifying screens 201 and 202 which promptly emit light as a direct function of X ray exposure.
  • the light recording latent image forming emulsion layer unit 115 is positioned adjacent this screen to receive the light which it emits. Because of the proximity of the screen 201 to the emulsion layer unit 115 only minimal light scattering occurs before latent image forming absorption occurs in this layer unit. Hence light emission from screen 201 forms a sharp image in emulsion layer unit 115.
  • crossover reducing layers 111 and 113 are interposed between the screen 201 and the remote emulsion layer unit and are capable of intercepting and attenuating this remaining light. Both of these layers thereby con­ tribute to reducing crossover exposure of emulsion layer unit 117 by the screen 201.
  • the screen 202 produces a sharp image in emulsion layer unit 117, and the light absorbing layers 111 and 113 simi­larly reduce crossover exposure of the emulsion layer unit 115 by the screen 202.
  • the crossover reduc­ing layers on opposite sides of the support can be used to absorb radiation from different regions of the spectrum.
  • a light absorbing dye can be present in one crossover reducing layer while an ultraviolet (UV) absorber is present in the remaining crossover reducing layer.
  • UV ultraviolet
  • the radiographic element 100 is removed from association with the intensifying screens 210 and 202 and processed in a conventional manner. That is, the radiographic element is brought into contact with an aqueous alkaline developer, such as a hydro­quinone-Phenidone®(1-phenyl-3-pyrazolidone) devel­oper having a pH of 10.0, a specific form of which is illustrated in the examples below.
  • the alkaline developer permeates the hydrophilic colloid layers, converting the silver halide emulsion layer latent image to a viewable silver image and simultaneously decolorizing the crossover reducing layers. Conven­tional post development steps, such as stop bath con­tact, fixing, and washing can occur.
  • the radio­graphic elements of this invention are fully compati­ble with conventional radiographic element process­ing, such as in an RP-X-Omat® processor.
  • the radiographic elements of the present invention offer advantages in crossover reduction by employing one or more crossover reducing layers com­prised a hydrophilic colloid employed as a dispersing vehicle and a particulate dye.
  • concentration of the dye present is chosen to impart an optical den­sity of at least 1.00 at the peak wavelength of emul­sion sensitivity. Since it is conventional practice to employ intensifying screen-radiographic element combinations in which the peak emulsion sensitivity matches the peak light emission by the intensifying screens, it follows that the dye also exhibits a den­sity of at least 1.00 at the wavelength of peak emis­sion of the intensifying screen.
  • particulate dyes including combinations of particulate dyes, capable of imparting a density of 1.00 or more over the entire spectral region of sig­nificant sensitivity and emission.
  • particulate dyes for radiographic elements to be used with blue emitting intensifying screens, such as those which employ calcium tungstate or thulium activated lanthanum oxybromide phosphors, it is generally preferred that the particulate dye be selected to produce an optical density of at least 1.00 over the entire spectral region of 400 to 500 nm.
  • the particulate dye exhibit a density of at least 1.00 over the spectral region of 450 to 550 nm. To the extent the wavelength of emission of the screens or the sensitivities of the emulsion lay­ers are restricted, the spectral region over which the particulate dye must also effectively absorb light is correspondingly reduced.
  • particulate dye optical densities of 1.00 chosen as described above are effective to reduce crossover to less than 10 percent, it is spe­cifically recognized that particulate dye densities can be increased until radiographic element crossover is effectively eliminated. For example, by increas­ing the particulate dye concentration so that it imparts a density of 10.0 to the radiographic ele­ment, crossover is reduced to only 1 percent.
  • the size of the dye particles is chosen to facilitate coating and rapid decolorization of the dye. In general smaller dye particles lend them­selves to more uniform coatings and more rapid decol­orization.
  • the dye particles employed in all instances have a mean diameter of less than 10.0 ⁇ m and preferably less than 1.0 ⁇ m. There is no theo­retical limit on the minimum sizes the dye particles can take.
  • the dye particles can be most conveniently formed by crystallization from solution in sizes ranging down to about 0.01 ⁇ m or less. Where the dyes are initially crystallized in form of particles larger than desired for use, conventional techniques for achieving smaller particle sizes can be employed, such as ball milling, roller milling, sand milling, and the like.
  • hydrophilic colloids can take any of vari­ous conventional forms, such as any of the forms set forth in Research Disclosure , Vol. 176, December 1978, Item 17643, Section IX. Vehicles and vehicle extenders, the hydrophilic colloid layers are most commonly gelatin and gelatin derivatives. Hydro­philic colloids are typically coated as aqueous solu­tions in the pH range or from about 5 to 6, most typically from 5.5 to 6.0, to form radiographic ele­ment layers.
  • the dyes which are selected for use in the practice of this invention are those which are capable of remaining in particulate form at those pH levels in aqueous solutions.
  • Dyes which by reason of their chromophoric make up are inherently ionic, such as cyanine dyes, as well as dyes which contain substituents which are ionically dissociated in the above-noted pH ranges of coating may in individual instances be sufficiently insoluble to satisfy the requirements of this inven­tion, but do not in general constitute preferred classes of dyes for use in the practice of the inven­tion.
  • dyes with sulfonic acid substitu­ents are normally too soluble to satisfy the require­ments of the invention.
  • nonionic dyes with carboxylic acid groups are in general insoluble under aqueous acid coating conditions. Specific dye selections can be made from known dye characteristics or by observing solubilities in the pH range of from 5.5 to 6.0 at normal layer coating temperatures ⁇ e.g., at a reference temperature of 40°C.
  • Preferred particulate dyes are nonionic polymethine dyes, which include the merocyanine, oxo­nol, hemioxonol, styryls, and arylidene dyes.
  • the merocyanine dyes include, joined by a methine linkage, at least one basic heterocyclic nucleus and at least one acidic nucleus.
  • Basic nuclei such as azolium or azinium nuclei, for exam­ple, include those derived from pyridinium, quinoli­nium, isoquinolinium, oxazolium, pyrazolium, pyrro­lium, indolium, oxadiazolium, 3H- or 1H-benzoindo­lium, pyrrolopyridinium, phenanthrothiazolium, and acenaphthothiazolium quaternary salts.
  • Exemplary of the basic heterocyclic nuclei are those satisfying Formulae I and II.
  • Z3 represents the elements needed to com­plete a cyclic nucleus derived from basic heterocy­clic nitrogen compounds such as oxazoline, oxazole, benzoxazole, the naphthoxazoles (e.g., naphth[2,1-d]­oxazole, naphth[2,3-d]oxazole, and naphth[1,2-d]oxa­zole), oxadazole, 2- or 4-pyridine, 2- or 4-quino­line, 1- or 3-isoquinoline, benzoquinoline, 1H- or 3H-benzoindole, and pyrazole, which nuclei may be substituted on the ring by one or more of a wide variety of substituents such as hydroxy, the halogens (e.g., fluoro, chloro, bromo, and iodo), alkyl groups or substituted alky
  • G1 represents an alkyl group or substituted alkyl group, an aryl or substituted aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a hydroxy group, an amino group, or a substituted amino group, wherein exemplary substituents can take the various forms noted in connection with Formulae VI and VII;
  • G2 can represent any one of the groups listed for G1 and in addition can represent a cyano group, an alkyl, or arylsulfonyl group, or a group represented by - -G1, or G2 taken together with G1 can represent the elements needed to complete a cyclic acidic nucleus such as those derived from 2,4-­oxazolidinone (e.g., 3-ethyl-N-(2-aminoxazolidinone)
  • Useful hemioxonol dyes exhibit a keto meth­ylene nucleus as shown in Formula III and a nucleus as shown in Formula IV.
  • G3 and G4 may be the same or different and may represent alkyl, substituted alkyl, aryl, substituted aryl, or aralkyl, as illustrated for R ring substitu­ents in Formula I or G3 and G4 taken together com­plete a ring system derived from a cyclic secondary amine, such as pyrrolidine, 3-pyrroline, piperidine, piperazine (e.g., 4-methylpiperazine and 4-phenylpip­erazine), morpholine, 1,2,3,4-tetrahydroquinoline, decahydroquinoline, 3-azabicyclo[3,2,2]nonane, indo­line, azetidine, and hexahydroazepine.
  • a cyclic secondary amine such as pyrrolidine, 3-pyrroline
  • Exemplary oxonol dyes exhibit two keto meth­ylene nuclei as shown in Formula III joined through one or higher uneven number of methine groups.
  • Useful arylidene dyes exhibit a keto methyl­ene nucleus as shown in Formula III and a nucleus as shown in Formula V joined by a methine linkage as described above containing one or a higher uneven number of methine groups.
  • G3 and G4 are as previously defined.
  • a specifically preferred class of oxonol dyes for use in the practice of the invention are the oxonol dyes satisfying Formula VI. wherein R1 and R2 each independently represent alkyl of from 1 to 5 carbon atoms.
  • Exemplary of specific preferred oxonol dyes are those set forth below in Table I.
  • a specifically preferred class of arylidene dyes for use in the practice of the invention are the arylidene dyes satisfying Formula VII.
  • A represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl substituent selected from the group consisting of 2-pyrazolin-5-­ones free of any substituent bonded thereto through a carboxyl group, rhodanines; hydantoins; 2-thiohydan­ toins; 4-thiohydantions; 2,4-oxazolidindiones; 2-­thio-2,4-oxazolidindiones; isoxazolinones; barbitu­rics; 2-thiobarbiturics and indandiones;
  • R represents hydrogen, alkyl of 1 to 4 carbon atoms or benzyl;
  • R1 and R2 each independently, represents alkyl or aryl; or taken together with R5, R6, N, and the carbon atoms to which they are attached rep
  • Exemplary of specific preferred arylidene dyes are those set forth below in Tables II and III.
  • UV absorber either blended with the dye in each of crossover reducing layers 111 and 113 or confined to one crossover reducing layer with the dye being confined to the other crossover reducing layer.
  • Any conventional UV absorber can be employed for this purpose.
  • Illustrative useful UV absorbers are those disclosed in Research Disclosure , Item 18431, cited above, Section V, or Research Dis­closure , Item 17643, cited above, Section VIII.C.
  • Preferred UV absorbers are those which either exhibit minimal absorption in the visible portion of the spectrum or are decolorized on processing similarly as the crossover reducing dyes.
  • the remaining features of the dual coated radiographic elements can take any convenient conventional form.
  • Such conventional radiographic element features are illustrated, for example, in Research Disclosure , Item 18431, cited above.
  • Other conventional features common to both silver halide radiographic elements and photographic elements are disclosed in Research Disclosure , Item 17643, cited above.
  • Radiographic elements according to this invention having highly desirable imaging character­istics are those which employ one or more tabular grain silver halide emulsions.
  • Preferred radiographic elements according to the present invention are those which employ one or more high aspect ratio tabular grain emulsions or thin, intermediate aspect ratio tabular grain emul­sions.
  • Preferred tabular grain emulsions for use in the radiographic elements of this invention are those in which tabular silver halide grains having a thick­ness of less than 0.5 ⁇ m (preferably less than 0.3 ⁇ m and optimally less than 0.2 ⁇ m) have an average aspect ratio of greater than 5:1 (preferably greater than 8:1 and optimally at least 12:1) and account for greater than 50 percent (preferably greater than 70 percent and optimally greater than 90 percent) of the total projected area of the silver halide grains present in the emulsion.
  • Preferred blue and minus blue spectral sensitizing dyes as well as optimum chemical and spectral sensitizations of tabular sil­ver halide grains are disclosed by Kofron et al U.S. Patent 4,439,520.
  • the preferred radiographic elements of this invention are those which employ one or more of the crossover reducing layers described above in combina­tion with tabular grain latent image forming emul­sions.
  • Preferred radiographic element and tabular grain silver halide emulsion features are disclosed in Abbott et al U.S. Patents 4,425,425 and 4,425,426 and Dickerson U.S. Patent 4,414,304.
  • Radiographic elements can be constructed according to this inven­tion in which tabular grain silver halide emulsion layers are coated nearer the support than nontabular grain silver halide emulsion layers to reduce cross­over, as illustrated by Sugimoto European Patent Application 0,084,637.
  • radiographic elements exhib­iting extremely low crossover levels can be achieved while also achieving high photographic speed, low levels of granularity, high silver covering power, and rapid processing capabilities deemed highly desirable in radiography.
  • the following examples compare the perfor­mance of double coated radiographic elements exposed using blue emitting thulium activating lanthanum oxy­bromide phosphor intensifying screens.
  • the radio­graphic elements were identical, except for the choice of the crossover reducing materials employed between the emulsion layer and the support on each major surface.
  • the dye satisfying the requirements of the invention was Dye 1/A shown above in Table II.
  • the dye was employed in a particulate form, the mean diameter of the dye particles being 0.08 ⁇ m.
  • C-1 Tartrazine Yellow
  • M-1 cationic mordant poly(1-methyl-2-vinylpyridinium p -­toluene sulfonate
  • CLS Carey Lea Silver
  • One control element was constructed with the same hydrophilic colloid layers, but without a cross­over reducing material being present. This element is referred to as C-0.
  • An emulsion layer was coated over each hydrophilic colloid layer.
  • the blue recording silver bromide emulsion layer was coated at a coverage of 2.2 g/m2 silver and 2.2 g/m2 gelatin.
  • hydrophilic colloid layers (including the emulsion layers) were hardened with bis(vinylsul­fonylmethyl) ether at 1.0% of the gelatin weight.
  • samples of the dual coated radiographic elements were exposed with a single intensifying screen placed in contact with one emulsion layer. Black paper was placed against the other emulsion side of the sample.
  • the X-radiation source was a Picker VTX653 3-phase X-ray machine, with a Dunlee High-Speed PX1431-CQ-150 kVp 0.7/1.4mm focus tube.
  • Exposure was made at 70 kVp, 32mAs, at a distance of 1.40 m. Filtration was with 3 mm Al equivalent (1.25 inherent + 1.75 al); Half Value Layer (HVL) - 2.6 mm Al. A 26 step Al wedge was used, differing in thickness by 2 mm per step.
  • Processing of the exposed film was in each instance undertaken using a processor commercially available under the trademrk Kodak RP X-Omat Film Processor M6A-N.
  • the developer employed exhibited the following formula: Hydroquinone 30 g Phenidone® 1.5 g KOH 21 g NaHCO3 7.5 g K2SO3 44.2 g Na2S2O5 12.6 g NaBr 35 g 5-Methylbenzotriazole 0.06 g Glutaraldehyde 4.9 g Water to 1 liter/ pH 10.0.
  • the film was in contact with the developer in each instance for less than 90 seconds.
  • the dye 1/A was entirely decolorized during processing. From Figure 2 it can be seen that the density of the element after processing was essen­tially similar to the element lacking a crossover reducing material. At the same time the capability of crossover reduction below 10 percent was demon­strated. Some loss of photographic speed was observed, but it is to be noted that, since the pur­pose of a crossover reducing agent is to prevent a portion of the light emitted by the screens from exposing the emulsion layers, some reduction in pho­tographic speed is inherent in crossover reduction.
  • This example demonstrates the satisfactory performance of a bleachable particulate dye to reduce crossover without producing dye stain in the pro­cessed radiographic element and with only minimal impact on imaging speed.
  • the control crossover reducing materials were unacceptable because of their high dye stain, and the control dye was unacceptable in producing an increased loss in imaging speed.
  • the control dye required the further incor­poration of a mordant, which added to the drying load on the processor. Without the mordant being present the imaging speed loss would have been significantly higher.
  • Examples 1 through 6 The procedure of Examples 1 through 6 was repeated, except that magenta dyes were substituted for testing, green sensitized radiographic emulsions were employed, and green emitting intensifying screens, Kodak Lanex Regular® screens, were employed.
  • the dye satisfying the requirements of the invention was Dye 4/A shown above the Table II.
  • the dye was employed in a particulate form, the mean diameter of the dye particles being 0.2 ⁇ m.
  • Acid Magenta (C.I. Acid Violet 19-C.I. 42,685), hereinafter referred to as C-2, was selected as a control exemplary of dyes which are water solu­ble and bleachable taught by the art to be used as a crossover reducing dye in a double coated radio­graphic element.
  • C-2 Acid Magenta
  • M-1 cationic mordant M-1 was employed in a 5 parts mor­dant to 1 part dye weight ratio.
  • C-3 1,3-Bis[1-(4-sulfonylphenyl)-3-carboxy-2-­pyrazolin-5-one-4] trimethine oxonol, disodium salt, hereinafter referred to as C-3, was selected as a control exemplary of magenta dyes which are water soluble and nonbleachable.
  • Dye C-3 differed from dye 10 disclosed on page 5 of U.K. Pat. Spec. 1,414,456 only in that the nuclei were joined by 3 methine groups instead of 5 (to shift absorption into the desired green spectral region). To reduce wandering of the dye cationic mordant M-1 was again employed in a 5 parts mordant to 1 part dye weight ratio.
  • the precipitate containing the dye was then purified through a number of washing and dissolu­tion/recrystallization steps.
  • the precipitate was first slurried in 500 ml refluxing glacial acetic acid, cooled to room temperature, filtered, washed with 250 ml acetic acid, 250 ml H2O, 250 ml metha­nol, and then dried. It was then dissolved in 100 ml hot dimethylsulfoxide and cooled to 40°C. 300 ml methanol was added, upon which a red precipitate formed, which was filtered, washed with methanol, acetone, and ligroin, and dried.
  • This precipitate was dissolved in 200 ml methanol and 6 ml (4.38 g) triethylamine and heated to reflux. 4.8 ml of con­centrated hydrochloric acid was added and a fine red precipitate was formed. The solution was filtered while hot and the precipitate was washed with metha­nol and acetone and dried. The precipitate was then dissolved in a refluxing mixture of 200 ml ethanol and 6.0 ml (4.38 g) triethylamine. 9.0 g of sodium iodide dissolved in 50 ml methanol was added. Upon cooling to room temperature, a red precipitate formed. The mixture was chilled in ice for one hour, then filtered. The precipitate was washed with etha­nol, ligroin and dried to yield the sodium salt of the dye.
  • the sodium salt of the dye was dissolved in 200 ml water with rapid stirring. 6.0 ml concen­trated hydrochloric acid was added and a fluffy red precipitate formed. The mixture was filtered and the precipitate was washed with water, methanol, acetone, and ligroin, and dried to yield Dye 1/O.

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  • Chemical & Material Sciences (AREA)
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EP19870311289 1986-12-23 1987-12-22 Radiographisches Element mit reduziertem Zwischenbildeffekt Expired EP0276566B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US94563486A 1986-12-23 1986-12-23
US73256 1987-07-13
US07/073,256 US4803150A (en) 1986-12-23 1987-07-13 Radiographic element exhibiting reduced crossover
US945634 1987-10-05

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EP0276566A1 true EP0276566A1 (de) 1988-08-03
EP0276566B1 EP0276566B1 (de) 1990-10-24

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EP0384634A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Schirm/Film-Konstruktionen mit verbesserter Quantendetektionsleistungsfähigkeit
EP0384633A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Elemente mit ausgewählten Empfindlichkeitsverhältnissen
EP0384753A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Elemente mit ausgewählten Kontrastverhältnissen
EP0391405A2 (de) * 1989-04-06 1990-10-10 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Verarbeitungsmethode dafür
EP0401709A2 (de) * 1989-06-05 1990-12-12 Fuji Photo Film Co., Ltd. Photographisches Röntgenmaterial
EP0449101A1 (de) * 1990-03-29 1991-10-02 Eastman Kodak Company Asymmetrische radiographische Elemente, Einrichtungen und Verpackungen
EP0456163A2 (de) * 1990-05-08 1991-11-13 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidmaterialien
EP0457153A1 (de) * 1990-05-08 1991-11-21 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial
EP0479160A1 (de) * 1990-10-01 1992-04-08 Eastman Kodak Company Diagnostische photographische Elemente mit verminderter Reflexion nach der Schnellentwicklung
EP0555897A1 (de) * 1992-02-14 1993-08-18 Agfa-Gevaert N.V. Photographisches Silberhalogenidröntgenmaterial mit passenden Bildton und Oberflächenglanz
EP0586749A1 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Farbstoffe mit lichtabsorption im tiefroten und infraroten Bereich des Spektrums
EP0586748A1 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Filterfarbstoffe für Schnellverarbeitungs-Verwendungen
EP0587230A2 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Filterfarbstoffe für Schnellverarbeitungs-Verwendungen
EP0587229A2 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Filterfarbstoffe für Schnellverarbeitungs-Verwendungen
EP0747760A1 (de) * 1995-05-22 1996-12-11 Eastman Kodak Company Radiographische Elemente mit minimalem Crossover-Effekt, die schnell verarbeitet werden können
EP1037101A1 (de) * 1999-03-18 2000-09-20 Fuji Photo Film Co., Ltd. Farbphotographisches photoempfindliches Silberhalogenidmaterial und Verfahren zur Bildherstellung
US7422843B2 (en) 2006-03-27 2008-09-09 Fujifilm Corporation Silver halide color photographic light-sensitive material
EP1832928A3 (de) * 2006-03-10 2009-01-28 Fujifilm Corporation Lichtempfindliches Aufzeichnungsmaterial, Flachdruckplattenvorläufer und Stapel davon
US7579139B2 (en) 2005-12-26 2009-08-25 Fujifilm Corporation Silver halide color photographic light-sensitive material

Families Citing this family (2)

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JPH02264936A (ja) * 1989-04-06 1990-10-29 Fuji Photo Film Co Ltd Ｘ線用ハロゲン化銀写真感光材料
JPH09230540A (ja) * 1996-02-26 1997-09-05 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びそれを用いた画像形成方法

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CA1148788A (en) * 1979-06-29 1983-06-28 Raymond G. Lemahieu Photographic silver halide materials containing dispersed light-absorbing merostyryl dyes

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DE2262794A1 (de) * 1971-12-21 1973-07-05 Fuji Photo Film Co Ltd Styrylfarbstoffe und verfahren zu ihrer herstellung

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Cited By (31)

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Publication number Priority date Publication date Assignee Title
EP0384633A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Elemente mit ausgewählten Empfindlichkeitsverhältnissen
EP0384753A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Elemente mit ausgewählten Kontrastverhältnissen
EP0384753A3 (de) * 1989-02-23 1990-10-31 Eastman Kodak Company Radiographische Elemente mit ausgewählten Kontrastverhältnissen
EP0384633A3 (en) * 1989-02-23 1990-10-31 Eastman Kodak Company Radiographic elements with selected speed relationships
EP0384634A3 (de) * 1989-02-23 1990-11-07 Eastman Kodak Company Radiographische Schirm/Film-Konstruktionen mit verbesserter Quantendetektionsleistungsfähigkeit
EP0384634A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Schirm/Film-Konstruktionen mit verbesserter Quantendetektionsleistungsfähigkeit
US5098818A (en) * 1989-04-06 1992-03-24 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing thereof
EP0391405A2 (de) * 1989-04-06 1990-10-10 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Verarbeitungsmethode dafür
EP0391405A3 (de) * 1989-04-06 1991-04-17 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Verarbeitungsmethode dafür
EP0401709A2 (de) * 1989-06-05 1990-12-12 Fuji Photo Film Co., Ltd. Photographisches Röntgenmaterial
EP0401709A3 (de) * 1989-06-05 1992-02-26 Fuji Photo Film Co., Ltd. Photographisches Röntgenmaterial
US5147769A (en) * 1989-06-05 1992-09-15 Fuji Photo Film Co., Ltd. X-ray photographic material
EP0449101A1 (de) * 1990-03-29 1991-10-02 Eastman Kodak Company Asymmetrische radiographische Elemente, Einrichtungen und Verpackungen
EP0456163A2 (de) * 1990-05-08 1991-11-13 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidmaterialien
EP0457153A1 (de) * 1990-05-08 1991-11-21 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial
EP0456163A3 (en) * 1990-05-08 1992-02-26 Fuji Photo Film Co., Ltd. Silver halide photographic materials
EP0479160A1 (de) * 1990-10-01 1992-04-08 Eastman Kodak Company Diagnostische photographische Elemente mit verminderter Reflexion nach der Schnellentwicklung
EP0555897A1 (de) * 1992-02-14 1993-08-18 Agfa-Gevaert N.V. Photographisches Silberhalogenidröntgenmaterial mit passenden Bildton und Oberflächenglanz
EP0587230A2 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Filterfarbstoffe für Schnellverarbeitungs-Verwendungen
EP0586748A1 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Filterfarbstoffe für Schnellverarbeitungs-Verwendungen
EP0586749A1 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Farbstoffe mit lichtabsorption im tiefroten und infraroten Bereich des Spektrums
EP0587229A2 (de) * 1992-09-11 1994-03-16 Agfa-Gevaert N.V. Filterfarbstoffe für Schnellverarbeitungs-Verwendungen
EP0587230A3 (en) * 1992-09-11 1995-12-27 Agfa Gevaert Nv Filter dyes for rapid processing applications
EP0587229A3 (en) * 1992-09-11 1995-12-27 Agfa Gevaert Nv Filter dyes for rapid processing applications
EP0747760A1 (de) * 1995-05-22 1996-12-11 Eastman Kodak Company Radiographische Elemente mit minimalem Crossover-Effekt, die schnell verarbeitet werden können
EP1037101A1 (de) * 1999-03-18 2000-09-20 Fuji Photo Film Co., Ltd. Farbphotographisches photoempfindliches Silberhalogenidmaterial und Verfahren zur Bildherstellung
US6489086B1 (en) 1999-03-18 2002-12-03 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive material and method for forming image
US7579139B2 (en) 2005-12-26 2009-08-25 Fujifilm Corporation Silver halide color photographic light-sensitive material
EP1832928A3 (de) * 2006-03-10 2009-01-28 Fujifilm Corporation Lichtempfindliches Aufzeichnungsmaterial, Flachdruckplattenvorläufer und Stapel davon
US7968271B2 (en) 2006-03-10 2011-06-28 Fujifilm Corporation Photosensitive recording material, planographic printing plate precursor, and stacks of the same
US7422843B2 (en) 2006-03-27 2008-09-09 Fujifilm Corporation Silver halide color photographic light-sensitive material

Also Published As

Publication number Publication date
EP0276566B1 (de) 1990-10-24
DE3765770D1 (de) 1990-11-29
CA1299424C (en) 1992-04-28
JPH01172828A (ja) 1989-07-07
JP2567434B2 (ja) 1996-12-25

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