EP0710879B1 - Produit radiographique - Google Patents

Produit radiographique Download PDF

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Publication number
EP0710879B1
EP0710879B1 EP19950420283 EP95420283A EP0710879B1 EP 0710879 B1 EP0710879 B1 EP 0710879B1 EP 19950420283 EP19950420283 EP 19950420283 EP 95420283 A EP95420283 A EP 95420283A EP 0710879 B1 EP0710879 B1 EP 0710879B1
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EP
European Patent Office
Prior art keywords
radiographic
optical brightener
product according
radiographic product
gelatin
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Expired - Lifetime
Application number
EP19950420283
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German (de)
English (en)
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EP0710879A1 (fr
Inventor
Gérard A.D. Friour
Françoise M. Thomas
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Eastman Kodak Co
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Kodak Pathe SA
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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • 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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images

Definitions

  • the present invention concerns silver halide photographic products which are associated with X-ray intensifying screens and used in radiography.
  • the invention concerns a radiographic system containing at least one layer of spectrally sensitised tabular grain silver halide emulsion and an intensifying screen.
  • the invention makes it possible to use a wide range of spectral sensitisers whilst avoiding the problem of residual colouring, also called “dye stain" in the art, in the areas of low exposure of the radiographic image.
  • radiography particularly in medical radiography, use is normally made of radiographic systems comprising an intensifying screen and a silver halide photosensitive product.
  • intensifying screens makes it possible to reduce the quantity of X-rays required to obtain a radiograph and consequently to reduce the quantity of X-rays absorbed by the patient.
  • Intensifying screens must have a maximum emission as close as possible to the sensitivity peak of the silver halide grains making up the radiographic film.
  • the silver halide photosensitive products used in radiography with intensifying screens comprise a transparent support coated on one of its faces, and preferably on both faces, with at least one layer of spectrally sensitised silver halide emulsion.
  • Silver halide grains are naturally sensitive to blue light, but, by adsorbing spectral sensitising dyes on their surface, they may have maximum absorption in the blue and/or green and/or red regions of the visible spectrum.
  • the spectral sensitising dye is chosen so that the maximum absorption of the silver halide grains occurs in the region of maximum emission of the intensifying screen.
  • a screen is used emitting in the blue region between 360 and 500 nm and a spectral sensitising dye in the blue region having maximum absorption in this range.
  • tabular grain silver halide emulsions can be used in radiographic products.
  • US patent 4,639,411 describes a radiographic element which comprises an emulsion consisting of tabular silver halide grains capable of forming a latent image when it is exposed to light.
  • This emulsion preferably consists of tabular grains with a thickness of less than 0.5 ⁇ m and an aspect ratio higher than 5:1.
  • Tabular grain emulsions require a high level of sensitising dye because of the high specific surface area of the grains.
  • Certain spectral sensitising dyes cause, in the radiographic image, a residual colouring in the areas which are unexposed or only slightly exposed. For example, the image then has yellow colouring in the areas of low density, if the dye is a spectral sensitiser in the blue region. This problem is particularly significant with fast processing which takes place in less than a minute and in which the time of immersion in the processing solution is very short.
  • the invention makes it possible to use spectral sensitising dyes which, if they were used alone in high quantities, would have caused a residual colouring in the areas of the image of low density. According to the invention, this colouring is avoided by associating therewith an optical brightener having special characteristics.
  • One advantage of the invention is that it affords a greater degree of freedom in the choice of spectral sensitising dyes.
  • the sensitometric properties of the radiographic image are not substantially impaired by the presence of the optical brightener according to the invention.
  • optical brighteners which have been known for a long time are substances which absorb ultraviolet light in the region of the spectrum lying between 300 and 400 nm and which are fluorescent in the blue region of the visible spectrum.
  • optical brighteners reduces the yellow appearance of the supporting polymer when a source of ultraviolet light is used.
  • the optical brightener is incorporated in a layer placed on the support, or on the support by soaking the support in a solution containing the optical brightener, for example a developing or fixing solution or a stabilising bath.
  • This article does not deal with the problem of the residual colouring due to the spectral sensitising dye.
  • US patent 4,232,112 describes a process for developing a colour photographic film in which the development solution or the bleaching/fixing solution comprises a bleaching agent which is a derivative of 4,4'-diamino-stilbene disulphonic acid and a second compound derived from benzene sulphonic or naphthalene sulphonic acid.
  • This process makes it possible to avoid on the one hand the residual colouring due to oxidation of the color developer in the bleaching/fixing solution and on the other hand the residual colouring which is due to the accumulation of various substances on the edges of the film.
  • US patent 4,587,195 describes a method for eliminating the residual colouring in a colour image.
  • a development solution comprising a combination of optical brighteners of the triazylstilbene type with slightly shifted absorption peaks.
  • US patent 5,238,793 describes a method of processing black and white films comprising a layer of silver halide emulsion spectrally sensitised with a cyanine dye.
  • the spectral sensitising dye forms in the processing solutions solid particles which adhere to the surface of the film and form specks or blotches on the final image.
  • the exposed film is placed in contact with a processing solution comprising a compound enabling the spectral sensitising dye to dissolve.
  • the solubilising compound is a stilbene derivative which is incorporated in the processing solution in which the formation of solid particles poses a problem, but it can also be in the photographic element. This possibility is not put into practice in this patent, which contains no disclosure relating to the location of the solubilising compound in the photographic element.
  • the problem of residual colouring resolved by the present invention is quite another matter, since it is due not to an accumulation of solid particles in the processing solution, but to the absorption of the residual spectral sensitising dye in the gelatin of the radiographic product.
  • a radiographic product comprising a support and at least one photosensitive layer comprising gelatin, at least one photosensitive silver halide tabular grain emulsion and a spectral sensitising dye in the blue region having an emission peak between 400 and 500 nm and present in the said radiographic product in sufficient quantity to cause, in the radiographic image, the formation of a residual yellow colouring due to the absorption of the aggregate of the residual dye in the gelatin, and an optical brightener
  • Anionic sulpho group means an ionised -SO 3 - group associated with a cation balancing the ionic charge by opposition to an acid group -SO 3 H.
  • Another object of the invention is a radiographic system comprising at least one X-ray intensifying screen with maximum emission between 360 and 500 nm and the radiographic product as defined above.
  • the emulsions used in the invention are emulsions with tabular grains of silver chloride, silver bromide, silver iodide or a mixture of these halides, in a binder.
  • the binder is a water-permeable hydrophilic colloid such as gelatin, gelatin derivatives, albumin, a polyvinyl alcohol, polyvinyl polymers, etc.
  • the emulsions may be hardened in accordance with one of the methods described in US patent 4,425,266.
  • the hardening agents which may be used are described in Research Disclosure, December 1989, No 308113, Section X.
  • the emulsions may comprise other compounds such as anti-fogging agents, stabilisers or anti-static agents.
  • the radiographic film may comprise an overcoat containing matting agents. This overcoat or the sensitive layer may contain plasticisers or lubricants. These compounds were described in Research Disclosure, Vol 184, August 1979, No 18431.
  • silver halide emulsions are preferably chemically sensitised by means of sulphur and/or gold and/or selenium, in accordance with the conventional chemical sensitisation methods described in Research Disclosure, December 1989, No 308119, Section III.
  • the emulsions are spectrally sensitised.
  • the conventional spectral sensitisation methods which can be used are described in Research Disclosure, December 1989, No 308119, Section IV.
  • the spectral sensitising dyes which can be used in the present invention are the blue spectral dyes which are liable to produce residual colouring, such as for example cyanine or merocyanine dyes. Cyanine dyes are described in Research Disclosure, December 1989, No 308119, Section IV A-C.
  • Cyanine dyes which can be used according to the invention correspond to the formula: where Z 1 and Z 2 represent the atoms necessary to complete a substituted or unsubtituted aromatic ring structure ; R 7 and R 8 each separately represent a substituted or unsubtituted alkyl radical having 1 to 12 carbon atoms, which may be substituted by a halogen, an alkoxy, aryl, aryloxy, sulpho or carboxyl radical; L 1 , L 2 and L 3 each separately represent a methine bond, substituted or unsubtituted; X is O, S, Se, -C- or N- and n is 0, 1 or 2.
  • cyanine dyes liable to produce a residual colouring are as follows:
  • optical brighteners which are used in the present invention must be capable of destroying the aggregate of the residual sensitising dye in the gelatin, which reduces the optical density corresponding to the residual colouring, giving rise to chemical species in which the wavelength of the absorption peak lies in a region of the visible spectrum where the sensitivity of the eye is low, preferably around the wavelengths below 420 nm.
  • these optical brighteners must have a sufficient number of solubilising groups to be able to be retained in the gelatin in the layers of the photographic product.
  • optical brighteners which can be used in the present invention are compounds of the stilbene type having at least three anionic sulpho groups.
  • the quantity of optical brightener is determined so that the residual colouring due to the spectral sensitising dye is highly attenuated without the sensitometric or physical properties of the radiographic product being impaired.
  • An appropriate quantity of optical brightener is between 0.05 and 2 mg/dm 2 and preferably between 0.5 and 1.5 mg/dm 2 .
  • radiographic systems In addition to the radiographic film, radiographic systems generally comprise a pair of X-ray intensifying screens situated on each side of the radiographic film.
  • the intensifying screens used in the invention have an emission peak in the blue or ultraviolet region whose wavelength is between 360 and 500 nm.
  • the X-ray intensifying screens comprise one or more luminophores in a mixture with a binder.
  • the luminophore particle size is generally between 0.5 and 20 ⁇ m and preferably between 1 and 10 ⁇ m.
  • Examples of luminophores emitting in the blue or ultraviolet region are calcium tungstate CaWO 4 , lanthane oxybromide LaOBr activated by terbium or thullium, gadolinium oxybromide activated by yttrium or cerium, YTaO 4 activated by gadolinium, bismuth, lead, cerium, barium fluorochloride BaFCl activated by europium, gadolinium, lanthanum or yttrium, or barium sulphate activated by europium or strontium.
  • binders are chosen from amongst the organic polymers transparent to light radiation and to X-rays, such as vinyl alcohol and o-sulphobenzaldehyde acetal polymers, chlorosulphonated polyethylenes, bisphenol polycarbonates, alkyl acrylate and methacrylate copolymers and polyurethanes.
  • Other binders which can be used within the scope of the invention are described in US patents 2,502,529, 2,887,379, 3,617,285, 3,300,310, 3,300,311 and 3,743 833 and in Research Disclosure, Vol 154, February 1977.
  • the preferred binders are polyurethanes such as Estane®, Permuthane® and Cargill®,
  • the X-ray intensifying screens may contain, in addition to the fluorescent layer, a protective layer and a reflective layer.
  • the films described in Examples 1-3 consist of an Estar® support coated, in the following order, with a layer of tabular grain silver bromide emulsion having a grain equivalent diameter of 2.14 ⁇ m and a mean grain thickness of 0.11 ⁇ m and an overcoat of gelatin.
  • the film also comprises a layer of gelatin placed between the emulsion layer and the support.
  • the film is hardened by means of bis(vinylsulphonylmethyl) ether, the amount of hardening agent by weight being equal to 2.25% of the total dry gelatin contained in the film.
  • the emulsion is optimally chemically sensitised by means of sulphur (150 mg KSCN per mole of Ag), gold (5.06 mg Na 3 (S 2 O 3 ) 2 Au,2 H 2 O per mole of Ag) and selenium (0.67 mg KSeCN per mole of Ag).
  • the emulsion is optimally spectrally sensitised with spectral sensitising dye A.
  • the samples of film are exposed to blue light simulating the exposure obtained through an intensifying screen.
  • the exposed films are then processed using a conventional RP-XOMAT® process in 90 seconds and a fast KRA® process in 45 seconds.
  • the residual colouring levels are measured by spectrophotometry at 440 nm (the wavelength corresponding to the absorption peak of the aggregate of the sensitising dye in the gelatin), the reciprocity failure for an exposure of between 1/50th and 5 seconds, the spectral sensitivity between 300 and 500 nm. In this way it is verified that no loss of sensitivity occurs in the near ultraviolet because of the absorbance of the optical brightener.
  • the resistance to pressure is estimated by using a pressure roller simulating mechanical stresses.
  • the optical brightener is put in the emulsion layer of the radiographic product.
  • a simplified format of radiographic product is used, as described above and comprising a colourless Estar R support, a tabular grain silver bromide emulsion (21 mg Ag/dm 2 , 2.85 mg/dm 2 gelatin, 465 mg of spectral sensitising dye A per mole of Ag), and an overcoat of gelatin (6.88 mg/dm 2 ).
  • 0.6 mg/dm 2 of optical brightener (Tinopal® or Phorwite®) is introduced into the emulsion layer either before spectral sensitisation (IF) or immediately after (AF).
  • IF spectral sensitisation
  • AF immediately after
  • the products are processed in automatic processors for the RP-XOMAT® and KRA® processes.
  • Figures 1 and 2 show the absorption spectrum between 350 and 500 nm.
  • the yellow residual dye due to the aggregate of the sensitising dye retained in the gelatin, corresponds to the principal peak situated at 440 nm. A less prominent peak can be seen, corresponding to the monomeric sensitising dye at around 410 nm.
  • Figures 3 and 4 show the optical density of the residual colouring at 440 nm for the RP-XOMAT® and KRA® processes.
  • 1-CHECK represents the check sample.
  • the method of introducing the optical brightener (before or after the spectral sensitising dye) is not critical.
  • the invention makes it possible to eliminate up to 82% of residual colouring in the RP-XOMAT® process and up to 90% of residual colour in the KRA® process without excessively impairing the sensitometric characteristics.
  • the optical brightener is located in a layer placed between the emulsion layer and the support. This arrangement may be useful where it is difficult to introduce the optical brightener into the emulsion layer for practical reasons or where interactions with other additives could occur.
  • a simplified format of radiographic product comprising, in the following order, a 20 mg/dm 2 gelatin layer between the support and the emulsion layer, a layer of tabular grain silver bromide emulsion (21 mg Ag/dm 2 , 32 mg/dm 2 gel) and an overcoat of gelatin (6.88 mg/dm 2 ).
  • a quantity of optical brightener (Tinopal® or Phorwite R ) of respectively 0.3, 0.6 and 1.2 mg/dm 2 is introduced.
  • Figures 5 and 6 show the absorption spectrum between 360 and 450 nm. It can be seen that the two compounds make it possible to reduce the residual colouring (lowering of the peak at 440 nm) and are more efficacious in the KRA® process.
  • Figure 7 shows the optical density at 440 nm, which corresponds to the residual colouring.
  • CHECK represents the control.
  • Tinopal R at a concentration of 1.2 mg/m 2 .
  • the invention makes it possible to eliminate up to 70% of residual colouring in the RP-XOMAT® process and up to 94% of residual colouring in the fast KRA® process without impairing the sensitometric characteristics.
  • Phorwite® 0.4 and 0.6 mg/dm 2 respectively is introduced into the gelatin overcoat.
  • Figure 8 shows the absorption spectrum between 350 and 500 nm, for the RP-XOMAT® process.
  • the best compromise enabling the residual colouring to be reduced without for all that modifying the sensitometric characteristics is obtained by putting the optical brightener in the gelatin layer of the photographic product placed between the emulsion layer and the support.
  • 90% of residual colouring is eliminated in the fast KRA® process and 67% of residual colouring in the RP-XOMAT® process with a concentration of Tinopal® of 1.2 mg/m 2 without the sensitometric characteristics being affected.
  • the normal format of radiographic film is used.
  • a blue Estar® support On both sides of a blue Estar® support, are coated, in the following order, a layer of tabular grain silver bromide emulsion (32 mg/dm 2 gel, 21 mg/dm 2 Ag), an intermediate layer of gelatin (3.54 mg/dm 2 gel) and an overcoat of gelatin (3.54 mg/dm 2 gel).
  • the film also comprises a layer of gelatin (14 mg/dm 2 gel) placed between the emulsion layer and the support.
  • the film is hardened by means of bis(vinylsulphonylmethyl) ether, the amount of hardening agent by weight being equal to 2.35% of the total dry gelatin contained in the film.
  • the emulsion is chemically sensitised and spectrally sensitised with spectral sensitising dye A as in Example 1.
  • Tinopal® 0.6 mg/dm 2 of Tinopal® is introduced into the emulsion after sensitisation.
  • the samples of film are exposed to blue light by means of a conventional Kodak X-Omat® intensifying screen.
  • the exposed films are then processed with an RP-XOMAT® process in 90 seconds and a KRA® process in 45 seconds, as in the previous examples.
  • the level of residual colouring is measured by spectrophotometry at 440 nm.
  • Tinopal R 1.2 mg/dm 2 of Tinopal R is introduced into the layer of gelatin placed between the support and the emulsion layer.
  • the samples of film are exposed and processed using the RP-XOMAT® process in 90 seconds and the KRA® process in 45 seconds, as in the previous example.
  • the level of residual colouring is measured by spectrophotometry at 440 nm.
  • Example 5 the best compromise enabling the residual colouring to be reduced without for all that modifying the sensitometric characteristics is obtained by placing the optical brightener in the gelatin layer of the photographic product placed between the emulsion layer and the support.
  • Example 5 up to 93.5% of residual colouring is eliminated in the fast KRA® process with a concentration of Tinopal® of 1.2 mg/m 2 without the physical and sensitometric characteristics being affected.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Conversion Of X-Rays Into Visible Images (AREA)

Claims (11)

  1. Produit radiographique comprenant un support et au moins une couche photosensible comprenant de la gélatine, au moins une émulsion à grains tabulaires d'halogénures d'argent photosensibles et un colorant sensibilisateur spectral dans le bleu présentant un pic d'émission entre 400 et 500 nm et présent dans ledit produit radiographique en quantité suffisante pour provoquer dans l'image radiographique la formation d'une coloration résiduelle jaune due à l'absorption de l'agrégat du colorant résiduel dans la gélatine, et un avivant optique,
    caractérisé en ce que l'avivant optique
    a) est un dérivé de l'acide 4,4'-diaminostilbène disulfonique présentant au moins 3 groupes sulfo anioniques,
    b) est placé dans au moins une des couches photosensibles du produit radiographique ou bien dans au moins une couche de gélatine située entre la couche photosensible et le support.
  2. Produit radiographique selon la revendication 1 dans lequel l'avivant optique est dans au moins une des couches photosensibles.
  3. Produit radiographique selon la revendication 1 dans lequel l'avivant optique est dans au moins une des couches de gélatine placées entre la couche photosensible et le support.
  4. Produit radiographique selon l'une quelconque des revendications 1 à 3 dans lequel l'avivant optique a pour formule:
    Figure 00320001
    où
    R1, R2, R3 et R4 sont chacun séparément choisis dans le groupe
    Figure 00330001
    halogène, hydrogène, hydroxy, alkyle substitué ou non, aryle substitué ou non, alcoxy substitué ou non, et sulfo,
    R5 et R6 sont chacun séparément choisis parmi l'hydrogène, alkyle substitué ou non et aryle substitué ou non,
    M est un cation équilibrant la charge ionique,
    avec la condition que le composé possède au moins un groupe solubilisant sulfo anionique sur R1, R2, R3 ou R4.
  5. Produit radiographique selon l'une quelconque des revendications 1 à 3 dans lequel l'avivant optique est choisi parmi les composés suivants :
    Figure 00330002
    ou
    Figure 00340001
  6. Produit radiographique selon la revendication 1 dans lequel la quantité d'avivant optique est comprise entre 0,05 et 2 mg/dm2.
  7. Produit radiographique selon la revendication 6 dans lequel la quantité d'avivant optique est comprise entre 0,5 et 1,5 mg/dm2.
  8. Produit radiographique selon la revendication 1 dans lequel le colorant sensibilisateur spectral est un colorant cyanine.
  9. Produit radiographique selon la revendication 8 dans lequel le colorant cyanine est choisi parmi :
    Figure 00340002
    Figure 00340003
    Figure 00350001
    Figure 00350002
    Figure 00350003
    Figure 00350004
    Figure 00360001
    Figure 00360002
    Figure 00360003
  10. Utilisation du produit radiographique selon l'une quelconque des revendications précédentes dans un procédé de développement rapide dont la durée totale du traitement est inférieure à une minute.
  11. Système radiographique comprenant au moins un écran renforçateur de rayons-X, ayant une émission maximale entre 360 et 500 nm et le produit radiographique selon l'une quelconque des revendications 1 à 9.
EP19950420283 1994-10-26 1995-10-16 Produit radiographique Expired - Lifetime EP0710879B1 (fr)

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FR9413051A FR2726378B1 (fr) 1994-10-26 1994-10-26 Produit radiographique
FR9413051 1994-10-26

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EP0710879A1 EP0710879A1 (fr) 1996-05-08
EP0710879B1 true EP0710879B1 (fr) 2000-12-13

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JP (1) JPH08211519A (fr)
DE (1) DE69519622T2 (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958666A (en) * 1997-09-10 1999-09-28 Eastman Kodak Company Photographic element containing antifogging cycanine dyes
JP3945938B2 (ja) * 1999-05-26 2007-07-18 富士フイルム株式会社 感光性ハロゲン化銀写真乳剤およびこれを含有するハロゲン化銀写真感光材料
KR100713710B1 (ko) * 1999-12-17 2007-05-07 (주)하야시바라 생물화학연구소 시아닌색소
KR20020028379A (ko) * 2000-10-09 2002-04-17 윤상진 침전물 자동 여과장치

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US5108887A (en) * 1989-09-22 1992-04-28 E. I. Du Pont De Nemours And Company Zeromethine merocyanine dyes as J-aggregating spectral sensitizers for tabular emulsions
EP0451813B1 (fr) * 1990-04-13 1997-03-26 Konica Corporation Matériau photographique à halogénure d'argent
US5238795A (en) * 1990-08-08 1993-08-24 Konica Corporation Light-sensitive silver halide photographic material
JPH06102606A (ja) * 1992-09-24 1994-04-15 Konica Corp ハロゲン化銀写真感光材料

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DE69519622D1 (de) 2001-01-18
FR2726378A1 (fr) 1996-05-03
DE69519622T2 (de) 2001-06-13
EP0710879A1 (fr) 1996-05-08
JPH08211519A (ja) 1996-08-20
FR2726378B1 (fr) 1999-05-07

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