US3237008A - Roomlight handling radiographic element including an x-ray sensitive layer overcoated with a dye desensitized silver halide emulsion - Google Patents

Roomlight handling radiographic element including an x-ray sensitive layer overcoated with a dye desensitized silver halide emulsion Download PDF

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US3237008A
US3237008A US83709A US8370961A US3237008A US 3237008 A US3237008 A US 3237008A US 83709 A US83709 A US 83709A US 8370961 A US8370961 A US 8370961A US 3237008 A US3237008 A US 3237008A
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silver halide
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light
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Dostes Claude
Maurice E Pfaff
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Eastman Kodak Co
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/167—X-ray
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/167—X-ray
    • Y10S430/168—X-ray exposure process

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  • This invention relates to photographic elements which have the light-sensitive layer or layers thereof protected from exposure to visible light. More particularly it relates to elements which are useful in obtaining X-ray photographs or radiograms. Still more particularly it relates to X-ray films which can be safely handled and processed under conditions of ordinary room-light illumination without exposure of the photosensitive layers thereof.
  • the element should also be stable against edge-fog without requiring special treatment or expensive extra handling of separate film sheets to employ special optical sealers, light-blocking cassettes, etc.
  • the roomlight handling elements should also be adapted to processing in conventional processing solutions without loss of optimum quality in the final result. It will be apparent from a reading of the present specification and claims that we have found, quite unexpectedly, a way to prepare roomlight handling photographic elements which meet each of the above requirements while at the same time allowing the operator to watch the complete development process under ordinary room light.
  • a further object is to provide roomlight handling radiographic elements which are stable against edge fog.
  • a still further object is to provide an element which can be processed in room light using conventional processing "ice solutions.
  • Another object is to provide roomlight handling radiographic elements which have light-blocking outer protective layers which permit observation of image development in ordinary room light.
  • Another and still further object is to provide such elements wherein the light-absorbing materials are readily removed in conventional fixing baths.
  • the roomlight handling radiographic element carries an outer emulsion layer which is a light-blocking layer for the inner-most light sensitive, X-ray sensitive emulsion layer.
  • the objects of the invention are accomplished by incorporating in each of the emulsion layers of the roomlight handling photographic element, a combination of a nitrogen-containing heterocyclic silver halide desensitizing compound and a yellow dye which absorbs a substantial portion of the visible radiation to which the silver halide is sensitive (i.e., radiation between about 350 and 500 mu).
  • the desensitizing compounds should be capable of strongly depressing the light sensitivity of the silver halide without appreciably alfecting the X-ray sensitivity.
  • the desensitized .silver halide grains should be readily removed from the layers of the radiographic elements in conventional processing baths.
  • the dyes used in each layer should also be readily removed or decolorized in conventional processing solutions.
  • the strongly desensitized silver halide should be readily removed in conventional processing solutions but not until development of the innermost layer has occurred. After roomlight processing, both the silver halide and the incorporated dye should be removed from .all layers or decolorized leaving a clearly visible radiographic image.
  • FIG. 1 shows a sectional view of a photographic element having a light-sealing backing layer
  • FIG. 2 shows an element which has an X-ray sensitive layer and a lightblocking layer on each side of the single support.
  • the visible-light absorbing dyes which are used in combination with the desensitizing compounds of this invention in the silver halide emulsion layers should advantageously be dyes which are stable in a colloid carrier and should advantageously be nondilfusing. To be suitable, they should be readily removable in the customary processing baths or be decolorized entirely by the con- (5)
  • S-pyrazolone dyes of the type suitable for use in the present invention comprise bis[1-(p-sulfophenyl)-3- methyl 5-pyrazolone-(4)]-methinoxonol; bis[1-(p-sulfophenyl) 3 methyl-5-pyrazolone-(4) ]trimethinoxonol; bis [3 methyl-1-p-su1fophenyl-S-pyrazolone-(4)-]pentamethinoxonol; and others as disclosed in US. Patent 2,852,386, issued September 16, 1958.
  • the yellow-colored dyes of Formulas 1 and 2 can be prepared by heating styryl quinoline containing a reactive methyl group with a substituted aromatic aldehyde in the presence of anhydrous zinc chloride in a sealed tube at 100 C. for several hours. After the heat treatment, the product is treated with hydrochloric acid and hot water, filtered and made alkaline with-ammonia. The precipitated styryl derivative of the base can then be recrystallized and converted to the salt by the addition of acid.
  • each silver halide emulsion layer of the roomlight handling element one or more of the desensitizing compoundswith one or more visible light-absorbing compounds, each of which are represented hereinabove.
  • the desensitizing compounds and the visible light-absorbing materials can be contained in combination in various concentrations in the layers of the roomlight handling radiographic elements.
  • a desensitizing compound in the order of from about 3.0 mg. to about 300 mg. per mole of silver halide.
  • the light-absorbing dye of the styryl-nucleus-containing type is added to the emulsion in a concentration in the order of from about 0.5 to about 5.0 grams per mole of silver halide and dyes of the S-pyrazolone type are added to the emulsion in the range from about 10 to about grams per mole of silver halide.
  • the outer-light-blocking protective layer normally comprises a silver halide emulsion layer more strongly desensitized than is the innermost light-sensitive layer.
  • an excess of desen sitizing compound this can be in the order of from about 20 mg. to 5.0 grams per mole of silver halide or more depending to some extent upon the desensitizing compound employed.
  • the visible light-absorbing dye is added in combination with the desensitizing compound in the emulsion in an amount from about 0.5 to about 5.0 grams per mole of silver halide for styryl-nucleus-containing dyes and from about 10 to 100 grams per mole of silver halide for the 5-pyrazolone dyes.
  • a suitable concentration of silver per square foot can vary from about 100 to about 900 mg. of silver per square foot.
  • the outer-light protecting emulsion layer can comprise a silver halide emulsion which forms latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott, U.S. Patent 2,592,250, issued April 8, 1952.
  • desensitizing compounds of the type herein described are incorporated in an amount in the range from about 25 mg. to about 250 mgv per mole of silver halide.
  • the light-absorbing dyes are contained in combination with desensitizing compounds in the range as indicated above for outer-lightblocking layers.
  • Silver halide emulsions which form latent images predominantly inside the silver halide crystal are also referred to as internal image emulsions and have been described in the co-pending application of Luckey et al., US. patent application Serial No. 786,225, filed January 12, 1959, now US. Patent 2,996,382, issued on August 15, 1961.
  • the internal image emulsions which are useful according to our invention have a reduced surface sensitivity.
  • Such internal image emulsions when measured according to normal photographic techniques by coating a test portion of the emulsion ion a transparent support, exposing to a light-intensity scale having a fixed time between 0.01 and 1 second, bleaching 5 minutes in a 0.3 percent p0- tassium ferricyanide solution at 65 F., and developing for about 5 minutes at 65 F. in developer B below, has a sensitivity, measured at a density of 0.1 above fog, appreciably greater (e.g., at least 1.4 log E greater) than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 F. in developer A below.
  • compositions A and B are given hereinafter.
  • Developer A is the usual type of surface image developer and developer B is an internal developer having high silver halide solvent activity.
  • Suitable internal image emulsions are described in Davey and Knott, US. Patent 2,592,250, issued April 8, 1962.
  • Other emulsions which can be used in the outermost layers of the present invention comprise, for example, relatively insensitive silver chlorobromide and silver bromoiodide emulsions.
  • the methods of incorporating the desensitizing compounds and visible light-absorbing materials in silver halide emulsions are well known to those skilled in the art.
  • the desensitizing compounds can be directly dispersed in the emulsions, or they can be dissolved in Water (or in organic solvents, such as methanol, ethanol, etc., where the water-solubility is not sufficiently great) and added in the form of their solutions.
  • the visible light-absorbing dyes can be directly dispersed in the emulsions, it is convenient to add the same in the form of solutions in appropriate solvents. Methanol, ethanol, pyridine, and the like have proved satisfactory for many of the dyes herein disclosed.
  • solvents e.g., pyridine diluted with methanol or acetone
  • the desensitizing compounds and the visible light-absorbing dyes are dispersed in the finished emulsions and should be uniformly distributed throughout the emulsions. The following procedure is satisfactory:
  • Stock solutions of the desensitizing compounds and visible light-absorbing dyes are prepared by dissolving the same in appropriate solvents as described above.
  • the desired amount of the stock solution of one of the dyes (or desensitizing compounds) is slowly added to the liquid gelatino-silver halide emulsion with stirring. Stirring is continued until the dye is thoroughly incorporated in the emulsion.
  • the desired amount of the stock solution of the desensitizing compound (or dye, if the desensitizing compound has been added first) is slowly added to the emulsion, while stirring. Stirring is continued until the second solution is thoroughly incorporated.
  • the treated emulsion can then be coated out on a suitable support, such as glass, cellulose derivative film, resin film, or paper, to suitable thicknesses and allowed to dry.
  • a suitable support such as glass, cellulose derivative film, resin film, or paper
  • the roomlight handling radiographic elements of our invention are duplicoated, i.e., coated on either side of a ,X-ray-sensitive layer of the multilayer radiographic elements prepared according to the invention can vary widelY, but in general thicknesses from about 0.4 to about 1.2
  • the thicknesses of the outer-protective layers are not critical and can depend more upon the concentration of the light diflusing, e.g., silver halide, and
  • EXAMPLE 1 To a liquid coarse grain gelatino-silver bromoiodide emulsion, prepared in the usual manner, was added per mole of silver halide, 50 mg. of Z-methyl-S-nitrobenzothiazole metho-p-toluenesulfonate (I) and 0.5 gram of 2-(2- methoxystyryl)quinoline hydrochloride (II). Thereafter the emulsion was coated at F. according to US. Patent 1,947,160, issued February 13, 1934, on both sides of an ordinary cellulose acetate film, and dried.
  • the resulting film was exposed to an 80 kv. X-ray source under roomlight illumination, developed in a bath of the composition of Table 1, fixed, and washed. All of the steps for processing of the roomlight handling radiographic element of this example were carried out under ordinary roomlight illumination.
  • the radiogram produced by this example was of good quality and did not show evidence of edge fog.
  • the speed of the innermost layer can advantageously be from about 50 to about times that of the outer-light blocking layer when developed in a surface developer, such as developer A above.
  • EXAMPLE 2 A clean cellulose acetate film base was coated according to Example 1 with a coarse grain silver 'bromoiodide emulsion prepared in the usual manner which had been desensitized with 43.5 mg. of 4-nitro-6-chlorobenzotriazole (I) and to which was added 25 grams of 3-carboxy 1- 1-sulfophenyl -4 (4"-sulfophenylazo -5-pyrazolone disodium salt (II) per mole of silver halide. The silver content of the coating was 882 mg. per square foot.
  • As an outer-light-blocking layer a fine-grain, silver bromoiodide emulsion strongly desensitized with 900 mg. of compound I and containing 80 grams of compound II per mole of silver halide was coated over each of the light-sensitive, X-ray-sensitive layers at a thickness to give 540 mg. of silver per square foot.
  • the coated film was handled for 15 minutes under 40-foot candles of cool light fluorescent illumination during exposure of the film to an 80 kv. X-ray source and developed in a developer composition of Example 1 to produce a radiogram of good contrast and speed and without the formation of edge fog.
  • the exposed and developed film was then fixed in a well-known manner, washed, and dried.
  • the resulting radiogram was of good quality and showed substantially no edge fog.
  • the innermost and outermost coatings of the roomlight-handling radiographic elements can contain other visible light-absorbing dyes.
  • merocyanine dyes such as those described by Brooker et al., U.S. Patent 2,493,747, issued January 10, 1950.
  • the outer light-absorbing pigments in the outer-lightblocking layers of our invention can also comprise lightabsorbing pigments such as zinc oxide, lead chromate, silver chromate, the silver salt of dyes derived from thiobarbituric acid as described by A. H. Herz in U.S. Patent 2,719,088, issued September 27, 1955, and tartrazine mordanted with polyvinyl pyrrolidone.
  • a light filtering layer between the innermost layer and the outermost protective layer to prevent ditfusion of additive materials which might otherwise become introduced into the innermost X-ray sensitive layer.
  • a suitable interlayer to prevent diifusion of acid dyes was found to comprise polyvinyl-a-rnethyl-allyl-N-quanidyl ketime and other suitable compounds in gelatin as described in U.S. Patent 2,882,156, issued April 14, 1959.
  • FIG. 1 the support is coated with a light-sensitive, X-ray-sensitive layer 11 which has coated thereon a light-blocking silver halide emulsion layer 12 which prevents the exposure of the light-sensitive layer 11 during roomlight handling of the radiographic element.
  • a light-sealing backing layer 13 On the back side of the element there is coated a light-sealing backing layer 13.
  • the backing layers suitably employed in the invention must be antihalation layers which dissolve smoothly in photographic developers and which do not disintegrate and contaminate conventional developer solutions, such as described in U.S. Patent 2,327,828, issued August 24, 1943.
  • the support 10 is coated on each side with an X-ray-sensitive, lightsensitive layer 11 and superimposed on each of the lightsensitive layers are the light-blocking silver halide emulsion layers 12.
  • a light-sealing backing layer is not used since the Outer protective layers protect the innermost layers 11 from visible light exposure.
  • a roomlight handling photographic element comprising a support having coated thereon at least one X- ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams of a nitrogen-containing heterocyclic silver halide desensitizing compound per mole of silver halide and a yellow dye selected from the group consisting of styryl-nucleus containing dyes at a concentration of about ,5 gram to 5 grams per mole of silver halide and 5-pyrazolone dyes at a concentration of about 10 grams to grams per mole of silver halide, and coated on said X-ray-sensitive layer at least one light-blocking gelatino-silver halide emulsion layer more strongly desensitized than said X-raysensitive layer and containing about 20 milligrams to 5 grams of a nitrogen-containing heterocyclic silverhalide desensitizing compound per mole of silver halide and a yellow dye selected from the group consisting of
  • a roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of a nitrogen-containing heterocyclic silver halide desensitizing compound and a yellow dye selected from the group consisting of styryl-nucleus containing dyes at a concentration of about .5 grams to 5 grams per mole of silver halide and S-pyrazolone dyes at a concentration of about 10 grams to 100 grams per mole of silver halide, and superimposed on each of said X-ray sensitive layers a light-blocking gelatino-silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide crystals more strongly desensitized than said X-ray-sensitive layers and containing about 25 milligrams to 250 milligrams per mole of silver halide of a nitrogen-
  • a roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of 2-methyl-5-nitrobenzothiazole metho-p-toluenesulfonate and about .5 gram to 5 grams per mole of silver halide of 2(2'-methoxystyryl)quino line hydrochloride, and superimposed on each of said X- ray-sensitive layers a light'blocking gelatino-silver halide emulsion layer that forms latent images predominantly inside the silver halide crystals more strongly desensitized than said X-ray-sensitive layers and containing about 20 milligrams to 5 grams per mole of silver halide of 2-methyl-S-nitrobenzothiazole metho-p-toluenesulfonate and about .5 gram to 5 grams per mole
  • a roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of 4-nitro-6-chlorobenzotriazole and about 10 grams to 100 grams per mole of silver halide of 3- carboxy 1-(1-su1fophenyl)-4 (4"-sulfophenylazo)-5-pyrazolone disodium salt, and having superimposed on each of said X-ray-sensitive layers a light-blocking gelatino-silver halide layer more strongly desensitized than said X-ray-sensitive layers containing about 20 milligrams to 5 grams per mole of silver halide of 4-nitro-6-chlorobenzotriazole and about 10 grams to 100 grams per mole of silver halide of 3-carboxy-l-(l'-sulfophenyl)-4-(4"- sulf
  • a roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of 6-ethoXy-2-(m-nitrostyryl)quinolinium ethylethosulfate and about .5 gram to 5 grams per mole of silver halide of 2(4'-methoxystyryl)quinoline hydrochloride, and having superimposed on each of said X-raysensitive layers .
  • a light-blocking gelatino-silver halide emulsion layer more strongly desensitized than said X- ray-sensitive layers containing about 20 milligrams to 5 grams per mole of silver halide of 6-ethoxy-2-(mnitrostyryl)quinolinium ethylethosulfate and about .5 gram to 5 grams per mole of silver halide of 2(4

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Description

Feb. 22, 1966 C. DOSTES ET AL ROOMLIGHT HANDLING RADIOGRAPHIG ELEMENT INCLUDING AN X-RAY SENSITIVE LAYER OVERCOATED WITH A DYE DESENSITIZED SILVER HALIDE EMULSION Filed Jan. 19, 1961 LIGHT-BLOCKING SILVER HAL/DE EMULSION LAYER X-RAY SENSITIVE LAYER SUPPORT 5A LIGHT SEALING BACKING LAYER LIGHT-BLOCKING SILVER HAL/DE EMULSION LAYER X-RAY SENSITIVE LAYER 8U P PORT -RAY SENSITIVE LAYER I LI6HT BLOCKING SILVER HAL/DE EMULSION LAYER Claude Dosies MauriceEPfaff' INVENTORS %MM ZQWZ ATTORNEYfi United States Patent 3,237,008 ROOMLIGHT HANDLING RADIOGRAPHIC ELE- MENT INCLUDING AN X-RAY SENSITIVE LAYER OVERCOATED WITH A DYE DESENSI- TIZED SILVER HALIDE EMULSIGN Claude Dostes, Joinville-le-Pont, Seine, and Maurice E. Pfatf, Eaubonne, Seine-et-Oise, France, assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey Filed Jan. 19, 1961, Ser. No. 83,709 5 Claims. (Cl. 25065) This invention relates to photographic elements which have the light-sensitive layer or layers thereof protected from exposure to visible light. More particularly it relates to elements which are useful in obtaining X-ray photographs or radiograms. Still more particularly it relates to X-ray films which can be safely handled and processed under conditions of ordinary room-light illumination without exposure of the photosensitive layers thereof.
There have been various methods proposed in the art for protecting the light-sensitive layer or layers of photographic elements used in obtaining X-ray photographs. Certain of these photographic elements have been provided with an opaque protecting medium which is removed after exposure in a special processing bath. Such protective layers have not been entirely satisfactory because the layers are diflicult to remove after exposure to X-rays and the light-blocking material is not always uniformly distributed throughout the medium. Other radiographic elements have been prepared using protective outer-layers, comprising a coating of chrome-yellow, Venetian red, and the like which forms a readily removable opaque protecting medium. This coating allows handling of the element in ordinary room light but is washed off prior to development so that development must of necessity be carried out in a darkroom. With any of the prior proposals for protecting the light-sensitive layer using an outer-protective opaque layer, there has also been the difficulty that these protective layers do not cover the edges of the film, and accordingly, light enters the film through these edges to produce edge-fog in the light-sensitive emulsion layer. To overcome this difficulty, it has been proposed to optically seal the edges of the film by applying a black colloid edge-coating or a sealing strip of opaque paper or fabric. It is apparent that the prior art has been unable to deduce a method for preparing a truly satisfactory roomlight handling photographic element. To meet the requirements of such an element, it should be stable to visible light exposure but have substantially unchanged sensitivity to X-ray radiation. The element should also be stable against edge-fog without requiring special treatment or expensive extra handling of separate film sheets to employ special optical sealers, light-blocking cassettes, etc. The roomlight handling elements should also be adapted to processing in conventional processing solutions without loss of optimum quality in the final result. It will be apparent from a reading of the present specification and claims that we have found, quite unexpectedly, a way to prepare roomlight handling photographic elements which meet each of the above requirements while at the same time allowing the operator to watch the complete development process under ordinary room light.
It is therefore an object of the present invention to provide a photographic element for X-rays which can be handled under conditions of ordinary roomlight illumination. A further object is to provide roomlight handling radiographic elements which are stable against edge fog. A still further object is to provide an element which can be processed in room light using conventional processing "ice solutions. Another object is to provide roomlight handling radiographic elements which have light-blocking outer protective layers which permit observation of image development in ordinary room light. Another and still further object is to provide such elements wherein the light-absorbing materials are readily removed in conventional fixing baths. Other objects will appear hereinafter.
According to the present invention the roomlight handling radiographic element carries an outer emulsion layer which is a light-blocking layer for the inner-most light sensitive, X-ray sensitive emulsion layer. The objects of the invention are accomplished by incorporating in each of the emulsion layers of the roomlight handling photographic element, a combination of a nitrogen-containing heterocyclic silver halide desensitizing compound and a yellow dye which absorbs a substantial portion of the visible radiation to which the silver halide is sensitive (i.e., radiation between about 350 and 500 mu). According to the present invention, the desensitizing compounds should be capable of strongly depressing the light sensitivity of the silver halide without appreciably alfecting the X-ray sensitivity. The desensitized .silver halide grains should be readily removed from the layers of the radiographic elements in conventional processing baths. The dyes used in each layer should also be readily removed or decolorized in conventional processing solutions. In the outermost light-blocking layer, the strongly desensitized silver halide should be readily removed in conventional processing solutions but not until development of the innermost layer has occurred. After roomlight processing, both the silver halide and the incorporated dye should be removed from .all layers or decolorized leaving a clearly visible radiographic image.
By reference to the accompanying drawing, there can be seen the manner in which the roomlight handling radiographic elements of our invention can be prepared. FIG. 1 shows a sectional view of a photographic element having a light-sealing backing layer, whereas FIG. 2 shows an element which has an X-ray sensitive layer and a lightblocking layer on each side of the single support.
The nitrogen-containing heterocyclic silver halide desensitizing compounds which are useful in the practice of our invention can advantageously be represented by the following structural formulas:
1 0 NO /S 2-methyl-5-nitrobenz0thiazole metho-p-toluenesulfonate l-methyl-S-nitroquinolinium methosulfate 4-nitro 6-ch1orobenzotriazole --C2Ha 6-ethoxy-2- (m-nitrostyryl) quinolinium ethylethosulfate 3,7-diamlno-5-pheny1-phenazinium chloride OzN 5-nitrobenzimidazole Additionaluseful nitrogen-containing hererocycles representative of the above classes comprise the following:
2- (o-nitrostyryl) -3 -ethylbenzothiazolium iodide, 2-.( o,p-dinitrostyr-yl) -benzotl1iazole, 6-nitro-benzo-1,2,3-triazole, 4-chloro-benzo-1,2,3-triazole,
OCHB CH=CH 01- (2) 2(4'-methoxystyryl) quinoline hydrochloride OH=CHO-CH3 c1- H (3) The condensation product from two molecular proportions of quinaldine methylsulfate and one molecular proportion of 4:4'-diphenyl dialdehyde in pyridine: The yellow-colored product of the probable formula:
CH=CH CH=CH N1 Q N: 5
CH3 H3 (4) The condensation product from two molecular proportions of quinaldine dimethylsulfate and one molecular proportion of azoxy benzalaniline in pyridine: The yellowcolored product of the probable formula:
S-chloro-benzo-l,2,3-triazole, 2-methyl-fi-nitrobenzothiazole metho-p-toluene sulfonate 2- (p-nitrostyryl) -quinoline metho-p-toluenesulfonate,
4- (p-nitrostyryl) -quinoline methoiodide, 1-ethyl-7-nitro-quinolinium ethylsulfate, 1,3-diamino-S-methylphenazinium chloride, 1,3-diamino-S-benZyIphenaZinium chloride, 3,7-diamino-5fi-hydroxy-ethylphenazium chloride, S-chlorobenzimidazole,
2-methyl-5-chlorobenzimidazole, Z-mercaptobenzimidazole, 2-mercapto-6-chlorobenzimidazole,' 4
The desensitizing compounds of the above type which can be advantageously employed in practicing our invention have been described in one or more of the following representative US. Patents: 2,400,872, May 28, 1946; 2,541,472, February 13, 1951; 2,939,789, June 7, 1960; 2,915,395, December 1, 1959; and 2,066,099, December 29, 1936.
The visible-light absorbing dyes which are used in combination with the desensitizing compounds of this invention in the silver halide emulsion layers should advantageously be dyes which are stable in a colloid carrier and should advantageously be nondilfusing. To be suitable, they should be readily removable in the customary processing baths or be decolorized entirely by the con- (5) The styryl-containing condensation product from quinaldine-methylsulfate and piperonal:
(6) The styryl-containing condensation product from quinaldine-methylsulfate and veratric aldehyde:
CH3 S 04- CH:OH OCH3 CHaSOF (7) The styryl-containing condensation product from quinaldine-methylsulfate and anisaldehyde:
yon=orro CH3 (8) The styryl-containing condensation product from 75 2-'methyl-3-methylbenzthiazole-methylsulfate with ,p-ami- CHaSOr no-benzaldehyde and reacted with undecoylchloride in the presence of pyridine and having the probable formula:
H2C S 10) 4 (phenylazo)-5-pyrazolone-3-carboxylic acid calcium salt having the formula:
prepared according to the disclosure of US. Patent 2,503,- 717, issued April 11, 1950.
11) 4,4 methenyl-bis-(1-naphthyl-3-methyl-pyrazolone-) of the formula:
u as
(12) 3 carboxy-1-(1'-sulfophenyl)-4-(4-sulfophenylazo -5-pyrazolone, disodium salt:
(I O O H i O=CN SOsNa Other S-pyrazolone dyes of the type suitable for use in the present invention comprise bis[1-(p-sulfophenyl)-3- methyl 5-pyrazolone-(4)]-methinoxonol; bis[1-(p-sulfophenyl) 3 methyl-5-pyrazolone-(4) ]trimethinoxonol; bis [3 methyl-1-p-su1fophenyl-S-pyrazolone-(4)-]pentamethinoxonol; and others as disclosed in US. Patent 2,852,386, issued September 16, 1958.
The yellow-colored dyes of Formulas 1 and 2 can be prepared by heating styryl quinoline containing a reactive methyl group with a substituted aromatic aldehyde in the presence of anhydrous zinc chloride in a sealed tube at 100 C. for several hours. After the heat treatment, the product is treated with hydrochloric acid and hot water, filtered and made alkaline with-ammonia. The precipitated styryl derivative of the base can then be recrystallized and converted to the salt by the addition of acid.
The light-absorbing compounds of the above type which can be advantageously employed in practicing our invention have been described herein or are described in one or more of the following representative patents: US. 2,274,- 782, March 3, 1942; 2,503,717, April 11, 1950; 2,058,725,
6 October 27, 1936; 2,186,731, January 9, 1940; 1,845,404, February 16, 1932; and British 399,387, October 5, 1933.
According to our invention, we incorporate in each silver halide emulsion layer of the roomlight handling element one or more of the desensitizing compoundswith one or more visible light-absorbing compounds, each of which are represented hereinabove. The desensitizing compounds and the visible light-absorbing materials can be contained in combination in various concentrations in the layers of the roomlight handling radiographic elements.
Ordinarily in the innermost layer which is X-ray sensitive and also light sensitive, we employ a desensitizing compound in the order of from about 3.0 mg. to about 300 mg. per mole of silver halide. The light-absorbing dye of the styryl-nucleus-containing type is added to the emulsion in a concentration in the order of from about 0.5 to about 5.0 grams per mole of silver halide and dyes of the S-pyrazolone type are added to the emulsion in the range from about 10 to about grams per mole of silver halide.
The outer-light-blocking protective layer normally comprises a silver halide emulsion layer more strongly desensitized than is the innermost light-sensitive layer. In the outermost layer, we normally employ an excess of desen sitizing compound, this can be in the order of from about 20 mg. to 5.0 grams per mole of silver halide or more depending to some extent upon the desensitizing compound employed. The visible light-absorbing dye is added in combination with the desensitizing compound in the emulsion in an amount from about 0.5 to about 5.0 grams per mole of silver halide for styryl-nucleus-containing dyes and from about 10 to 100 grams per mole of silver halide for the 5-pyrazolone dyes. In the outer-light-blocking emulsion layer a suitable concentration of silver per square foot can vary from about 100 to about 900 mg. of silver per square foot.
The outer-light protecting emulsion layer can comprise a silver halide emulsion which forms latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott, U.S. Patent 2,592,250, issued April 8, 1952. Where emulsions of this type are used according to the invention, desensitizing compounds of the type herein described are incorporated in an amount in the range from about 25 mg. to about 250 mgv per mole of silver halide. In such emulsion layers the light-absorbing dyes are contained in combination with desensitizing compounds in the range as indicated above for outer-lightblocking layers.
Silver halide emulsions which form latent images predominantly inside the silver halide crystal are also referred to as internal image emulsions and have been described in the co-pending application of Luckey et al., US. patent application Serial No. 786,225, filed January 12, 1959, now US. Patent 2,996,382, issued on August 15, 1961. The internal image emulsions which are useful according to our invention have a reduced surface sensitivity. Such internal image emulsions, when measured according to normal photographic techniques by coating a test portion of the emulsion ion a transparent support, exposing to a light-intensity scale having a fixed time between 0.01 and 1 second, bleaching 5 minutes in a 0.3 percent p0- tassium ferricyanide solution at 65 F., and developing for about 5 minutes at 65 F. in developer B below, has a sensitivity, measured at a density of 0.1 above fog, appreciably greater (e.g., at least 1.4 log E greater) than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 F. in developer A below.
The developer compositions which are used in defining an internal image emulsion by comparison with a conventional surface image emulsion developer, compositions A and B are given hereinafter. Developer A is the usual type of surface image developer and developer B is an internal developer having high silver halide solvent activity.
The following developer compositions are used in the method of determining relative internal sensitivity of preferred emulsions:
(A): Grams N-methyl-p-aminophenol sulfate 0.31 Sodium sulfite, desiccated 39.6 Hydroquinone 6.0 Sodium carbon-ate, desiccated 18.7 Potassium bromide 0.86 Citric acid 0.68 Potassium metabisulfite 1.5 Water'to make 1.0 liter.
N-methyl-p-aminophenol sulfate 2.0 Sodium sulfite, desiccated 90.0 Hydroquinone 8.0 Sodium carbonate, monohydrate 52.5 Potassium bromide 5.0 Sodium thiosulfate 10.0
Water to make 1.0 liter.
Suitable internal image emulsions are described in Davey and Knott, US. Patent 2,592,250, issued April 8, 1962. Other emulsions which can be used in the outermost layers of the present invention comprise, for example, relatively insensitive silver chlorobromide and silver bromoiodide emulsions.
The methods of incorporating the desensitizing compounds and visible light-absorbing materials in silver halide emulsions are well known to those skilled in the art. The desensitizing compounds can be directly dispersed in the emulsions, or they can be dissolved in Water (or in organic solvents, such as methanol, ethanol, etc., where the water-solubility is not sufficiently great) and added in the form of their solutions. While the visible light-absorbing dyes can be directly dispersed in the emulsions, it is convenient to add the same in the form of solutions in appropriate solvents. Methanol, ethanol, pyridine, and the like have proved satisfactory for many of the dyes herein disclosed. Mixtures of solvents, e.g., pyridine diluted with methanol or acetone, can also be used. According to the invention the desensitizing compounds and the visible light-absorbing dyes are dispersed in the finished emulsions and should be uniformly distributed throughout the emulsions. The following procedure is satisfactory:
Stock solutions of the desensitizing compounds and visible light-absorbing dyes are prepared by dissolving the same in appropriate solvents as described above. The desired amount of the stock solution of one of the dyes (or desensitizing compounds) is slowly added to the liquid gelatino-silver halide emulsion with stirring. Stirring is continued until the dye is thoroughly incorporated in the emulsion. Then the desired amount of the stock solution of the desensitizing compound (or dye, if the desensitizing compound has been added first) is slowly added to the emulsion, while stirring. Stirring is continued until the second solution is thoroughly incorporated. The treated emulsion can then be coated out on a suitable support, such as glass, cellulose derivative film, resin film, or paper, to suitable thicknesses and allowed to dry. Most usually the roomlight handling radiographic elements of our invention are duplicoated, i.e., coated on either side of a ,X-ray-sensitive layer of the multilayer radiographic elements prepared according to the invention can vary widelY, but in general thicknesses from about 0.4 to about 1.2
mils, can be used. The thicknesses of the outer-protective layers are not critical and can depend more upon the concentration of the light diflusing, e.g., silver halide, and
absorbing materials per square foot of coated surface.
The following examples will serve to illustrate further the present invention.
EXAMPLE 1 To a liquid coarse grain gelatino-silver bromoiodide emulsion, prepared in the usual manner, was added per mole of silver halide, 50 mg. of Z-methyl-S-nitrobenzothiazole metho-p-toluenesulfonate (I) and 0.5 gram of 2-(2- methoxystyryl)quinoline hydrochloride (II). Thereafter the emulsion was coated at F. according to US. Patent 1,947,160, issued February 13, 1934, on both sides of an ordinary cellulose acetate film, and dried.
On either side of the coated support in the same manner an internal image emulsion was coated which was prepared according to the disclosure of US. Patent 2,592,- 250, issued April 8, 1952, into which had been added with stirring 50 mg. of compound I and 0.5 gram of compound II per mole of silver halide. The additions to the emulsion were made while holding at 90 F. The emulsion composition was coated at 90 F. at a thickness to give 600 mg. of silver halide per square foot, and dried.
The resulting film was exposed to an 80 kv. X-ray source under roomlight illumination, developed in a bath of the composition of Table 1, fixed, and washed. All of the steps for processing of the roomlight handling radiographic element of this example were carried out under ordinary roomlight illumination. The radiogram produced by this example was of good quality and did not show evidence of edge fog.
In the present invention the speed of the innermost layer can advantageously be from about 50 to about times that of the outer-light blocking layer when developed in a surface developer, such as developer A above.
Table 1 Water at F cc 500 N-methyl-p-aminophenolsulfate grams 2.0 Sodium sulfite (dessicated) do 90.0 Hydroquinone do 8.0 Sodium carbonate monohydrate do 52.5 Potassium bromide do 5.0 Water to make 1.0 liter.
EXAMPLE 2 A clean cellulose acetate film base was coated according to Example 1 with a coarse grain silver 'bromoiodide emulsion prepared in the usual manner which had been desensitized with 43.5 mg. of 4-nitro-6-chlorobenzotriazole (I) and to which was added 25 grams of 3-carboxy 1- 1-sulfophenyl -4 (4"-sulfophenylazo -5-pyrazolone disodium salt (II) per mole of silver halide. The silver content of the coating was 882 mg. per square foot. As an outer-light-blocking layer a fine-grain, silver bromoiodide emulsion strongly desensitized with 900 mg. of compound I and containing 80 grams of compound II per mole of silver halide was coated over each of the light-sensitive, X-ray-sensitive layers at a thickness to give 540 mg. of silver per square foot.
After drying the coated film was handled for 15 minutes under 40-foot candles of cool light fluorescent illumination during exposure of the film to an 80 kv. X-ray source and developed in a developer composition of Example 1 to produce a radiogram of good contrast and speed and without the formation of edge fog.
EXAMPLE 3 -nitrostyryl)quinolinium ethylethosulfate (I) and to which was added 2.5 grams of 2-(4'-methoxystyryl)quinoline hydrochloride (II) per mole of silver halide. The silver content of the coating was 750 mg. per square foot.
U.S. Patent 2,592,250- was desensitized with 50 mg. of-
Table 2 Grams N-methyl-p-aminophenolsulfate 2.2 Hydroquinone 8.8 Sodium sulfite (anhydrous) 72.0 Sodium carbonate (crystalline) 130.0 Potassium bromide 4.0
Water to make 1.0 liter.
The exposed and developed film was then fixed in a well-known manner, washed, and dried. The resulting radiogram was of good quality and showed substantially no edge fog.
Alternatively, the innermost and outermost coatings of the roomlight-handling radiographic elements can contain other visible light-absorbing dyes. For example: merocyanine dyes such as those described by Brooker et al., U.S. Patent 2,493,747, issued January 10, 1950. The outer light-absorbing pigments in the outer-lightblocking layers of our invention can also comprise lightabsorbing pigments such as zinc oxide, lead chromate, silver chromate, the silver salt of dyes derived from thiobarbituric acid as described by A. H. Herz in U.S. Patent 2,719,088, issued September 27, 1955, and tartrazine mordanted with polyvinyl pyrrolidone. In accordance With our invention, it is possible to use a light filtering layer between the innermost layer and the outermost protective layer to prevent ditfusion of additive materials which might otherwise become introduced into the innermost X-ray sensitive layer. For example, a suitable interlayer to prevent diifusion of acid dyes was found to comprise polyvinyl-a-rnethyl-allyl-N-quanidyl ketime and other suitable compounds in gelatin as described in U.S. Patent 2,882,156, issued April 14, 1959.
Our invention will now be described by reference to the accompanying drawing. In FIG. 1 the support is coated with a light-sensitive, X-ray-sensitive layer 11 which has coated thereon a light-blocking silver halide emulsion layer 12 which prevents the exposure of the light-sensitive layer 11 during roomlight handling of the radiographic element. On the back side of the element there is coated a light-sealing backing layer 13. The backing layers suitably employed in the invention must be antihalation layers which dissolve smoothly in photographic developers and which do not disintegrate and contaminate conventional developer solutions, such as described in U.S. Patent 2,327,828, issued August 24, 1943.
In FIG. 2 of the accompanying drawing'the support 10 is coated on each side with an X-ray-sensitive, lightsensitive layer 11 and superimposed on each of the lightsensitive layers are the light-blocking silver halide emulsion layers 12. In roomlight handling element of the type shown in FIG. 2, a light-sealing backing layer is not used since the Outer protective layers protect the innermost layers 11 from visible light exposure.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A roomlight handling photographic element comprising a support having coated thereon at least one X- ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams of a nitrogen-containing heterocyclic silver halide desensitizing compound per mole of silver halide and a yellow dye selected from the group consisting of styryl-nucleus containing dyes at a concentration of about ,5 gram to 5 grams per mole of silver halide and 5-pyrazolone dyes at a concentration of about 10 grams to grams per mole of silver halide, and coated on said X-ray-sensitive layer at least one light-blocking gelatino-silver halide emulsion layer more strongly desensitized than said X-raysensitive layer and containing about 20 milligrams to 5 grams of a nitrogen-containing heterocyclic silverhalide desensitizing compound per mole of silver halide and a yellow dye selected from the group consisting of styrylnucleus containing dyes at a concentration of about .5 gram to 5 grams per .mole of silver halide and 5-pyrazolone dyes at a concentration of about 10 grams to 100 grams per mole of silver halide, said yellow dye being absorbent in the regions of the visible spectrum in which said gelatino-silver halide emulsions are sensitive and suitable to transmit the rest of the visible spectrum so that the progress of development of said X-ray-sensitive layer can be observed in roomlight.
2. A roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of a nitrogen-containing heterocyclic silver halide desensitizing compound and a yellow dye selected from the group consisting of styryl-nucleus containing dyes at a concentration of about .5 grams to 5 grams per mole of silver halide and S-pyrazolone dyes at a concentration of about 10 grams to 100 grams per mole of silver halide, and superimposed on each of said X-ray sensitive layers a light-blocking gelatino-silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide crystals more strongly desensitized than said X-ray-sensitive layers and containing about 25 milligrams to 250 milligrams per mole of silver halide of a nitrogen-containing heterocyclic silver halide desensitizing compound and a yellow dye selected from the group consisting of styryl-nucleus containing dyes at a concentration of about .5 gram to 5.0 grams per mole of silver halide and 5-pyrazolone dyes at a concentration of about 10 grams to 100 grams per mole of silver halide, said yellow dye being absorbent in the regions of the visible spectrum in which said gelatino silver halide emulsions are sensitive and suitable to transmit the rest of the visible spectrum so that the progress of development of said X-ray-sensitive layers can be obserbed in roomlight.
3. A roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of 2-methyl-5-nitrobenzothiazole metho-p-toluenesulfonate and about .5 gram to 5 grams per mole of silver halide of 2(2'-methoxystyryl)quino line hydrochloride, and superimposed on each of said X- ray-sensitive layers a light'blocking gelatino-silver halide emulsion layer that forms latent images predominantly inside the silver halide crystals more strongly desensitized than said X-ray-sensitive layers and containing about 20 milligrams to 5 grams per mole of silver halide of 2-methyl-S-nitrobenzothiazole metho-p-toluenesulfonate and about .5 gram to 5 grams per mole of silver halide of 2(2'-methoxystyryl) quinoline hydrochloride, said yellow dye being absorbent in the regions of the visible spectrum in which said gelatino-silver halide emulsions are sensitive and suitable to transmit the rest of the visible spectrum so that the progress of development of said X- ray-sensitive layer can be observed in roomlight,
4. A roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of 4-nitro-6-chlorobenzotriazole and about 10 grams to 100 grams per mole of silver halide of 3- carboxy 1-(1-su1fophenyl)-4 (4"-sulfophenylazo)-5-pyrazolone disodium salt, and having superimposed on each of said X-ray-sensitive layers a light-blocking gelatino-silver halide layer more strongly desensitized than said X-ray-sensitive layers containing about 20 milligrams to 5 grams per mole of silver halide of 4-nitro-6-chlorobenzotriazole and about 10 grams to 100 grams per mole of silver halide of 3-carboxy-l-(l'-sulfophenyl)-4-(4"- sulfophenylazo)-5-pyrazolone disodium salt, said yellow dye being absorbent in the regions of the visible spectrum in which said gelatino-silver halide emulsions are sensitive and suitable to transmit the rest of the visible spectrum so that the progress of development of said X- ray-sensitive layer can be observed in roomlight.
5. A roomlight handling photographic element comprising a support having coated on both sides thereof an X-ray-sensitive gelatino-silver halide emulsion layer containing about 3 milligrams to 300 milligrams per mole of silver halide of 6-ethoXy-2-(m-nitrostyryl)quinolinium ethylethosulfate and about .5 gram to 5 grams per mole of silver halide of 2(4'-methoxystyryl)quinoline hydrochloride, and having superimposed on each of said X-raysensitive layers .a light-blocking gelatino-silver halide emulsion layer more strongly desensitized than said X- ray-sensitive layers containing about 20 milligrams to 5 grams per mole of silver halide of 6-ethoxy-2-(mnitrostyryl)quinolinium ethylethosulfate and about .5 gram to 5 grams per mole of silver halide of 2(4'-methoxystyryl)quinoline hydrochloride, said yellow dye being absorbent in the regions of the visible spectrum in which said gelatino-silver halide emulsions are sensitive and suitable to transmit the rest of the visible spectrum so that the progress of development of said X-ray-sensitive layer can be observed in roomlight.
References Cited by the Examiner UNITED STATES PATENTS 2,090,607 8/ 1937 Baldsiefen 96101 2,098,442 11/1937 Troland 96108 2,503,717 4/1950 Fierke et al. 9684 2,541,472 2/1951 Kendall et al. 96101 2,542,304 2/1951 Boucher 25068 2,592,250 4/1952 Davey et al. 9694 2,725,296 11/1955 Kendall 9668 2,759,822 8/ 1956 Jones et al. 9668 2,853,386 9/1958 Tong 96114 2,882,156 4/1959 Minsk 96114 3,114,833 12/1963 Fine 9668 FOREIGN PATENTS 230,964 2/1911 Germany. 334,878 3/ 1921 Germany.
NORMAN G. TORCHIN, Primary Examiner.
RALPH G. NILSON, Examiner.

Claims (1)

1. A ROOMLIGHT HANDLING PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING COATED THEREON AT LEAST ONE XRAY-SENSITIVE GELATINO-SILVER HALIDE EMULSION LAYER CONTAINING ABOUT 3 MILLIGRAMS TO 300 MILLIGRAMS OF A NITROGEN-CONTAINING HETEROCYCLIC SILVER HALIDE DESENTIZING COMPOUND PER MOLE OF SILVER HALIDE AND A YELLOW DYE SELECTED FROM THE GROUP CONSISTING OF STYRYL-NUCLEUS CONTAINING DYES AT A CONCENTRATION OF ABOUT .5 GRAM TO 5 GRAMS PER MOLE OF SILVER HALIDE AND5-PYRAZOLONE DYES AT A CONCENTRATION OF ABOUT 10 GRAMS TO 100 GRAMS PER MOLE OF SILVER HALIDE, AND COATED ON SAID X-RAY-SENSITIVE LAYER AT LEAST ONE LIGHT-BLOCKING GELATINO-SILVER HALIDE EMULSION LAYER MORE STRONGLY DESENSITIZED THAN SAID X-RAYSENSITIVE LAYER AND CONTAINING ABOUT 20 MILLIGRAMS TO 5 GRAMS OF A NITROGEN-CONTAINING HETEROCYCLIC SILVER HALIDE DESENSITIZING COMPOUND PER MOLE OF SILVER HALIDE AND A YELLOW DYE SELECTED FROM THE GROUP CONSISTING OF STYRYLNUCLEUS CONTAINING DYES AT A CONCENTRATION OF ABOUT .5 GRAM TO 5 GRAMS PER MOLE OF SILVER HALIDE AND 5-PYRAZOLONE DYES AT A CONCENTRATION OF ABOUT 10 GRAMS TO 100 GRAMS PER MOLE OF SILVER HALIDE, SAID YELLOW DYE BEING ABSORBENT IN THE REGIONS OF THE VISIBLE SPECTRUM IN WHICH SAID GELATINO-SILVER HALIDE EMULSIONS ARE SENSITIVE AND SUITABLE TO TRANSMIT THE REST OF THE VISIBLE SPECTRUM SO THAT THE PROGRESS OF DEVELOPMENT OF SAID X-RAY-SENSITIVE LAYER CAN BE OBSERVED IN ROOMLIGHT.
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US3510348A (en) * 1966-03-11 1970-05-05 Eastman Kodak Co Direct positive recording film
US3515559A (en) * 1966-09-30 1970-06-02 Minnesota Mining & Mfg Dry process proof sheet composition
US3630744A (en) * 1966-07-01 1971-12-28 Agfa Gevaert Nv Selectively desensitized silver halide emulsion materials
US3658547A (en) * 1969-03-07 1972-04-25 Fuji Photo Film Co Ltd Silver halide photographic emulsions containing phenozine-n-oxides desensitizers
US3935529A (en) * 1974-10-09 1976-01-27 United Technologies Corporation Modulated energy conservative current supply
FR2324026A1 (en) * 1975-09-10 1977-04-08 Minnesota Mining & Mfg PHOTOGRAPHIC ELEMENTS THAT CAN BE MANIPULATED IN LIGHT
US4472497A (en) * 1983-02-18 1984-09-18 Minnesota Mining And Manufacturing Company White light handleable photographic materials
US5041364A (en) * 1990-10-01 1991-08-20 Eastman Kodak Company Diagnostic photographic elements exhibiting reduced glare following rapid access processing
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EP0754972A1 (en) * 1995-07-18 1997-01-22 Agfa-Gevaert N.V. X-ray silver halide photographic material suitable for maintenance in bright darkroom lighting conditions
US20050123440A1 (en) * 2003-12-09 2005-06-09 Eastman Kodak Company Sensor for contaminants

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US5041364A (en) * 1990-10-01 1991-08-20 Eastman Kodak Company Diagnostic photographic elements exhibiting reduced glare following rapid access processing
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