US3809906A - Radiographic colour material - Google Patents

Radiographic colour material Download PDF

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Publication number
US3809906A
US3809906A US00303385A US30338572A US3809906A US 3809906 A US3809906 A US 3809906A US 00303385 A US00303385 A US 00303385A US 30338572 A US30338572 A US 30338572A US 3809906 A US3809906 A US 3809906A
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United States
Prior art keywords
radiographic
silver halide
colour
emulsion
halide emulsion
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Expired - Lifetime
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US00303385A
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English (en)
Inventor
Doorselaer M Van
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Agfa Gevaert NV
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Agfa Gevaert NV
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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

Definitions

  • ABSTRACT A radiographic silver halide colour emulsion for the production of a radiographic monochromic dye image by the steps of radiographic exposureand colour development, said exposure proceeding in contact with an X-ray intensifying screen emitting for at least 50 percent light of the wavelength region beyond 410 nm and having a main emission maximum in the green region of the spectrum, the said emulsion comprising a mixture of a silver halide-emulsion capable of producing a visible image upon said exposure and colour development, and a relatively low speed silver chloridecontaining emulsion, the speed of which is insufficient -to produce a visible, image by the said exposure and development, and incorporating at least one colour coupler producing by coupling with an oxidized aromatic primary amino colour developing agent a monochromic dye image, characterized in that said emulsion is spectrally sensitized for the: wavelength region comprised between 480 and 600 nm'.
  • the present invention relates to green-sensitized radiographic silver halide colour emulsions for radiographic exposure in contact with intensifying screens, the luminescent substances of which have a high emission in the green spectral wavelength region.
  • the exposed radiographic silver halide materials should. be processed in a minimum of time.
  • radiographic elements which preferably comprise a colourless support and at least one silver halide emulsionlayer, each such layer containing at least one colour coupler producing by coupling with an oxidized aromatic primary amino developing agent a monochromic dye image mainly absorbing in the red and green spectral regions.
  • Radiographic colour images which have certain advantages'over black-and-white radiographs, e.g., in that they offer more visual retrieval of information and have a lower silver halide content, normally cannot be producedwith satisfactory quality by rapid colour processing at elevated temperature because the gradation, especially in the higher densities, is much lower than that obtainable at ambient temperatures, which results in colour images of unsatisfactory quality.
  • radiographic silver hal ide materials in contact with intensifying screens comprising luminescent substances emitting in the U.V. or blue region of thespectrum.
  • intensifying fluorescence screens used together with the radiographic silver halide materials are in practice almost exclusively screens that comprise calcium 'tugnstate or lead/barium sulphate as phosphor, because the skilled art worker has never questioned the superiority of these screens over the large variety of screens comprising other types of U.V.- or blue-emittingphosphors.
  • the radiographic silver halide emulsions used .have their optimum sensitivity in the U.V. and blue regions of the spectrum.
  • a second object of the present invention is to provide a radiographic colour material that can be processed automatically after exposure at elevated temperaturein less than 2 minutes.
  • Another object of the present invention is toprovide a radiographic material, the spectral sensitivity of which has been extended beyond the U.V.-blue region of the spectrum so that it can be used for exposure in contact with intensifying screens comprising luminescent substances emitting in the green region of the spectrum.
  • a radiographic colour emulsion for radiographic exposure in contact with an X-ray intensifying screen emitting for at least 50 percentligm of the wavelength region beyond 410 nm, and having a main fluorescence emission maximum in the green region of the spectrum, the said emulsion comprising a mixtureof a silver halide emulsion, capable of producing a visible image upon said exposure and colour development, and a sliver chloride-containing emulsion, the speed of which is insufficient .to producea visible image upon the said exposure and development, and incorporating at least i one colour coupler producing by coupling with an oxidized aromatic primary amino developing-agent a monochromic dye image, wherein the said emulsion is spectrally sensitized for the green wavelength region comprised between 480 and 600 nm.
  • the invention further provides a radiographic recording combination, which comprises a radiographic silver halide material having a support and a greensensitized radiographic colour emulsion as described above, and an intensifying screen, which during radiographic exposure is in contact with the said emulsion,
  • the said intensifying screen comprising luminescent material spectrally emittingfor atleast 50 percent in the wavelength region beyond 410 nm and having a the green reand oxychlorideactivated with terbium or dysprosium, lanthanum and gadolinium oxysulphides activated with terbium or with terbium and dysprosium, or with europium or europium and samarium and yttrium and lutetium Oxysulphide activated with one of the above rare earth elements.
  • Rare earth luminescent materials have been extensively described in the recent literature for which we refer, e.g., to German Pat. No. 1,282,819; French Pat. Nos.
  • the said screens may be arranged separately from the radiation-sensitive silver halide material or it may formwith the silver halide emulsion an integral arrangement so that on one and the same support both the silver halide emulsion and the X-ray intensifying screen are provided.
  • the radiographic material may be a singleor double-coated radiographic material which means that the radiographic material comprises either at only one side or at both sides of the support a radiation-sensitive silver halide emulsion.
  • the intensifying screens may be provided at both sides of a single or double coated radiographic material.
  • the radiographiccombination ofintensifying screens and radiographic colour materials may further comprise the common intermediate and/or protective and/or stripping layers, which may be arranged between or over the radiation sensitive emulsions and the intensifying screens.
  • the radiographic silver halide emulsion is formed by adding to the image-forming silver halide emulsion a silver chloride-containing emulsion having such a sufficiently low speed that no visible image is produced therein under the conditions of exposure and development of the radiographic imageforming silver halide emulsion;
  • the blue-light sensitivity of the image-forming silver halide emulsion is preferably at least 100 times the blue-light sensitivity of the silver chloride-containing emulsion.
  • the amount of low speed silver chloridecontaining emulsion to be added to the image-forming silver halide emulsion may vary within very wide limits, the ratio of low speed silver chloride to image-forming silver halide, expressed in parts by weight of silver ni-.
  • the low-speed silver chloride-containing emulsion is preferably a fine-grain silver chloride-containing emulsion having a particle size in the range from 50 to 500 nm.
  • a pure silver chloride emulsion as low speed emulsion it is also possible to use an emulsion of mixed silver halides comprising silver chloride, e.g., a silver chlorobromide emulsion.
  • the radiographic silver halide emulsion according to the presentinvention which comprises a mixture of image-forming silver halide and non-image forming silver chloride, is spectrally sensitized for the wavelength region comprised between 480 nm and 600 nm.
  • spectral sensitization maximum is preferably comprised between 520 nm and 560 nm.
  • the spectral sensitization of the radiographic silver halide emulsion of the present invention should be such that the sensitivity of the emulsion for the dark-room illumination is kept as low as possible. If necessary or desired, selectively working desensitizing dyes could be incorporated in the emulsion to lower the sensitivity for the darkroom illumination.
  • the emulsions can be spectrally sensitized by any of the accepted procedures. They can be spectrally sensitized by means of any of the common spectrally sensitizing dyes used in silver halide emulsions, particularly.
  • the image-forming radiographic silver halide emulsion may comprise different types of silver halide, e.g., silver chloride, silver bromide, silver chlorobromide, and silver chlorobromoiodide.
  • the image-forming silver halide emulsion is preferably a medium or high speed image-forming silver halide emulsion in which the silver halide is predominantly silver bromide, e.g., pure silver bromide emulsions and silver bromoiodide emulsions, the iodide content of which is less than 10 mole percent.
  • the average silver halide grain size is preferably comprised between 500 nm and 1200 nm.
  • the total silver halide content in the mixed silver halide emulsion is generally such that after coating on a suitable support the amount of silver halide, expressed support. 1
  • the monochromic radiographic dye image preferably has its main absorption in the red region (600-700 nm) of the visible spectrum and it absorbs in the green region (500-600 nm) of the visible spectrum for at least 30 percent in respect of the red region. In other words cyan dye images with a fairly large sideabsorption in the-green region and blue dye images are favoured.
  • phenol or a-naphthol type colour couplers that on colour development of the silver halide with an aromatic primary amino developing agent form a quinoneimine dye mainly absorbing in the red and green and having an absorption maximum in the spectral wavelength range of 550 to 700, are particularly suitable.
  • Phenol couplers having such properties correspond, e.g., to the following general formula:
  • R and R each represent a carboxylic acid acyl or sulphonic acid acyl group includingsaid groups in substituted state, e,'g., an aliphatic carboxylic acidacyl' group, an'aromaticcarboxylic acid acyl group, an
  • heterocycliccarboxylic acid acyl group e.g., a 2-furoyl 5 group ora 2-thienoyl group, an aliphatic sulphonic acid acyl group, an aromatic sulphonic acid acyl group, a sulphonyl thienyl group, an aryloxy-substituted aliphatic carboxylic'acid acyl group, aphenyl carbamyl aliphatic carboxylic acid acyl group, or a tolyl carboxylic acid acyl group.
  • the image-forming silver halide emulsion can be chemically sensitized by any of the accepted procedures,
  • the emulsions can be digested with naturally active gelatin or with small amounts of sulphur containing compounds such as allyl thiocyanate, ally] thiourea, so-
  • the image formingemulsion' can also be sensitized. by means of reductors, e.g., tin
  • R represents a hydrogen atom, an alkyl, a carboxy, or an alkoxycarbonyl' group, such as 5 -methyl-7- hydroxy-s triazolofl ,5 -a pyrimidine.
  • additives e.g., hardening agents such as formaldehyde, dialdehydes, hydroxy aldehydes, mucochloric and mucobromic acid, acrolein, and glyoxal, mordanting agentsfor anionic colour couplers or dyes formed therefrom, e.g., as described in British conts a hydrogen atom, an al- 5 potassium chloroaurate, and potassium auritbiocyasulphonic acids, carbo ryalltylated polyethyleneglycol 1 *ethers or esters as described" in French Pat. No.
  • iso-C,,H -C H 1,537,417 such as (OCH CH OCHCOONa, fluorinated surfactants,
  • starch and polymethylmethacrylate particles can be present in one or more of the hydrophilic colloid layers, of the radiation-sensitive silver halideelemjentsof thepresent invention.
  • U.V.-absorbing compounds may be incorporated inthe support orin h ydrophilic colloid intermediate layers of the radiographic element.
  • the radiographic silver halide colour elements of the present invention are developed, afterradiographic exposure, preferably in an energetic surface developer.
  • the highenergy is requiredin order to allow the development to proceed quickly. It can be obtainedby properly alkalizing the developing liquid (pH 9-12), by
  • aromatic primary amino colour developing agents to pending application Ser. No. 42381/71, plasticizers and 6 coatingfaids, e.g., saponin, e.g., dialkylsulphosuccinic acid salts such as sodium diisooctylsulphosuccinate, alkylaryl polyether sulphuric acids, alkylarylpolyetherobtain an increased rate of colour development (see, e.g., German Pat. No; 954,311 and French Pat. No.
  • development accelerators can be used either in thesilver halide emulsion or in the developing bath. They include -hydroxy-l ,2,3,4 tetrahydroquinoline, l-
  • alkylene oxide compounds of various types e.g., alkylene oxide condensation products or polymers as described in US. Pat. Nos. 1,970,578, 2,240,472 2,423,549, 2,441,389, 2,531,832 and 2,533,990 and in UK. Pat. Nosv 920,637, 940,051, 945,340, 991,608 and 1,015,023.
  • Other development accelerating compounds are onium and polyonium compounds preferably of the ammonium, phosphonium, and sulphonium type for example trialkyl sulphonium salts such as dimethyl-n-nonyl sulphonium p-toluene sulphonate, tetraalkyl ammonium salts such as dodecyl trimethyl ammonium p-toluene sulphonate, alkyl pyridinium and alkyl quinolinium salts such as l-m-nitrobenzyl quinolinium chloride and l-dodecyl pyridinium chloride, bisalkylene pyridinium salts such as N,N-tetramethylene bispyridinium chloride, quaternary ammonium and phosphonium polyoxyalkylene salts especially polyoxyalkylene bispyridinium salts, examples of which can be found in U.S. Pat. No. 2,944,900, etc.
  • the developing solutions can also comprise any of the usual additional ingredients, e.g., sodium sulphite and hydroxylamine or derivatives thereof, hardening agents, antifoggants, for instance, benzotriazole, nitrobenzimidazole, S-nitro-indazole, halides such as potassium bromide, silver halide solvents, toning and intensifying compounds, solvents, e.g., dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone for chemical ingredients that are difficult to dissolve in the preparation of the developing solutions or that tend to precipitate upon standing, etc.
  • additional ingredients e.g., sodium sulphite and hydroxylamine or derivatives thereof
  • hardening agents e.g., benzotriazole, nitrobenzimidazole, S-nitro-indazole, halides such as potassium bromide, silver halide solvents, toning and intensifying compounds
  • solvents e.g., dimethylformamide, dimethylace
  • the development step need not be followed by a bleaching step so that a processing as simple as that for producing black-and-white radiographs can be applied.
  • the exposed radiographic colour elements of the present invention are preferably processed in an automatic processing apparatus for X-ray films, in which the photographic material can be guided automatically and at a constant speed from one processing unit to the other.
  • Example A radiographic colour material was prepared in the following way.
  • the low speed silver chloride emulsion was prepared by adding an aqueous solution of silver nitrate to an aqueous gelatin/sodium chloride solution, precipitating the gelatin emulsion with ammonium sulphate, washing and peptizing. Gelatin was then added as well as 5- methyl-7-hydroxy-s-triazolo[l,5-a]pyrimidine so that no chemical ripening occurred.
  • the mean grain size of the silver chloride emulsion was 220 nm.
  • the emulsion was diluted to make 920 ml and then coated on both sides of a subbed polyethylene terephthalate support, the total surface of which is 10 sq.m. (2 X 5 sq.m). On both sides a gelatin anti-abrasion layer of 0.0015 mm was provided, whereupon the radiographic colour material formed was dried.
  • the spectrally sensitized material has a sensitization maximum at about 540 nm. 7
  • a non-spectrally sensitized material prepared in identical circumstances but without the addition of the spectrally sensitizing dye as well as the spectrally sensitized material were arranged between two fluorescent intensifying screens comprising as luminescent material gadolinium oxysulphide activated with terbium-and the radiographic elements formed were exposed to 60 kV X-ray radiation through a lead bar test object in order to determine the relationship between speed and MTF- value.
  • the radiographic colour materials were colour-processed automatically, which includes colour-development (24 sec at 41C), fixing (20 sec at 41 C), rinsing (25 sec at 41 C) and drying (20 sec at 55 C).
  • the developing bath used had a pHof 10.6 and comprised per litre: 8 g of N-hydroxyethyl-N-ethyl-pphenylene diamine, 1.5 g of hydroxylamine, 4 g of anhydrous sodium sulphite, 1 g of potassium bromide, and 65 g of anhydrous potassium carbonate. Fixing occurred by means of a sodium thiosulphate fixing solution.
  • each of R and R is a carboxylic or sulphonic acid acyl group.
  • a radiographic recording element comprising the combination of a radiographic silver halide material having a support and on at least one side thereof a spectrally sensitized silver halide emulsion according to claimJ with at least one X-ray intensifying screen, which during radiographic exposure isin contact with the said emulsion, the said intensifying screen comprising luminescent material spectrally emitting for at least 50 percent in the wavelength region beyond 410 nm and having a main fluorescence emission maximum in the green region of the spectrum.
  • a radiographic recording element wherein the said luminescent material is a rare earth oxysulphide or oxyhalide activated with other selected rare earths.
  • a radiographic recording element wherein the said luminescent material is a gadolinium or lanthanum oxysulphide or oxyhalide activated with erbium, terbium, or dysprosium or with terbium and dysprosium or is anyttrirum or lutetium oxysulphide activated with a rare earth element.
  • a radiographic recording element wherein the said luminescent material has a main fluorescence emission peak in the region comprised between 520 and 560 nm.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Conversion Of X-Rays Into Visible Images (AREA)
US00303385A 1971-11-05 1972-11-03 Radiographic colour material Expired - Lifetime US3809906A (en)

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GB5162871A GB1414455A (en) 1971-11-05 1971-11-05 Radiographic colour material

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US (1) US3809906A (ja)
JP (1) JPS5841502B2 (ja)
BE (1) BE790862A (ja)
CA (1) CA1000101A (ja)
DE (1) DE2254306C2 (ja)
FR (1) FR2158575B1 (ja)
GB (1) GB1414455A (ja)
IT (1) IT970200B (ja)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986007170A1 (en) * 1985-05-29 1986-12-04 The Cancer Institute Board Method and apparatus for high energy radiography
US5576154A (en) * 1994-06-28 1996-11-19 Sterling Diagnostic Imaging, Inc. Photographic recording materials for medical radiography

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6041901A (ja) * 1983-08-19 1985-03-05 山崎　長之助 カフスボタン
JPS61113307U (ja) * 1984-12-11 1986-07-17
DE3614476A1 (de) * 1986-04-29 1987-11-12 Du Pont Deutschland Aufzeichnungssystem fuer die strahlentherapie
JP4369876B2 (ja) 2004-03-23 2009-11-25 富士フイルム株式会社 ハロゲン化銀感光材料および熱現像感光材料
US20060057512A1 (en) 2004-09-14 2006-03-16 Fuji Photo Film Co., Ltd. Photothermographic material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807725A (en) * 1954-01-27 1957-09-24 Gerard Lemeac Vigneau Color radiography process
FR2120950A5 (ja) * 1971-01-05 1972-08-18 Agfa Gevaert Nv

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152907A (en) * 1959-11-12 1964-10-13 Eastman Kodak Co Method for controlling speed and contrast of photographic emulsions
US3734735A (en) * 1969-08-22 1973-05-22 Agfa Gevaert Nv Colour radiography

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807725A (en) * 1954-01-27 1957-09-24 Gerard Lemeac Vigneau Color radiography process
FR2120950A5 (ja) * 1971-01-05 1972-08-18 Agfa Gevaert Nv

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986007170A1 (en) * 1985-05-29 1986-12-04 The Cancer Institute Board Method and apparatus for high energy radiography
US4868399A (en) * 1985-05-29 1989-09-19 The Cancer Institute Board Method and apparatus for high energy radiography
US5576154A (en) * 1994-06-28 1996-11-19 Sterling Diagnostic Imaging, Inc. Photographic recording materials for medical radiography

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Publication number Publication date
FR2158575A1 (ja) 1973-06-15
JPS4855730A (ja) 1973-08-04
DE2254306A1 (de) 1973-05-10
FR2158575B1 (ja) 1978-01-06
DE2254306C2 (de) 1984-06-20
JPS5841502B2 (ja) 1983-09-12
CA1000101A (en) 1976-11-23
BE790862A (nl) 1973-04-30
GB1414455A (en) 1975-11-19
IT970200B (it) 1974-04-10

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