EP1376616B1 - Method for producing X-ray images using a binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer - Google Patents
Method for producing X-ray images using a binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer Download PDFInfo
- Publication number
- EP1376616B1 EP1376616B1 EP20030101862 EP03101862A EP1376616B1 EP 1376616 B1 EP1376616 B1 EP 1376616B1 EP 20030101862 EP20030101862 EP 20030101862 EP 03101862 A EP03101862 A EP 03101862A EP 1376616 B1 EP1376616 B1 EP 1376616B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- phosphor
- screen
- panel
- phototimer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 86
- 238000003860 storage Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 3
- 229910052799 carbon Inorganic materials 0.000 title description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 99
- 229920000052 poly(p-xylylene) Polymers 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 15
- 230000005855 radiation Effects 0.000 description 14
- 230000000149 penetrating effect Effects 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000013047 polymeric layer Substances 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000002601 radiography Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000009607 mammography Methods 0.000 description 2
- 238000009659 non-destructive testing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- OOLUVSIJOMLOCB-UHFFFAOYSA-N 1633-22-3 Chemical group C1CC(C=C2)=CC=C2CCC2=CC=C1C=C2 OOLUVSIJOMLOCB-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 241001505523 Gekko gecko Species 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002178 europium compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
- G21K2004/04—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens with an intermediate layer
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
- G21K2004/06—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens with a phosphor layer
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
- G21K2004/10—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens with a protective film
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
- G21K2004/12—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens with a support
Definitions
- This invention relates to a method for exposing an object to X-rays comprising the use of a binderless phosphor screen with a support including an amorphous carbon (a-C) layer.
- a-C amorphous carbon
- a well-known use of phosphors is in the production of X-ray images.
- an X-ray radiograph is obtained by X-rays transmitted image-wise through an object and converted into light of corresponding intensity in a so-called intensifying screen (X-ray conversion screen) wherein phosphor particles absorb the transmitted X-rays and convert them into visible light and/or ultraviolet radiation to which a photographic film is more sensitive than to the direct impact of X-rays.
- a special type of phosphor is used, known as a photostimulable phosphor, which being incorporated in a panel or screen, is exposed to incident pattern-wise modulated X-ray beam and, as a result thereof, temporarily stores energy contained in the X-ray radiation pattern.
- a beam of visible or infra-red light scans the panel or screen to stimulate the release of stored energy as light that is detected and converted to sequential electrical signals which can be processed to produce a visible image.
- the phosphor should store as much as possible of the incident X-ray energy and emit as little as possible of the stored energy until stimulated by the scanning beam. This is called “digital radiography” or “Computed Radiography” (CR).
- a “phototimer” comprises a radiometer for measuring the radiation dose passing through the object (patient) and the radiographic imaging system and a connection to the source of penetrating radiation for switching the penetrating radiation source off as soon as a pre-set dose is reached.
- a phototimer it is important that a well measurable dose reaches the radiometer in the phototimer, since when the dose reaching the phototimer is too low, the reproducibility of the off-switching of the source of penetrating radiation is not what it should be from the point of view of image quality.
- the imaging system should itself only absorb penetrating radiation up to such an extent as is necessary for good speed and image quality so that - with a patient dose as low as possible and only dictated by the examination at hand - the radiometer is reached by a sufficiently high exposure dose for reproducible off-switching of the source of penetrating radiation.
- the amount of radiation that reaches the "phototimer" is determined by the absorption of penetrating radiation by the object, the tube side of the cassette containing the storage phosphor panel or screen and the back side of the cassette.
- the absorption of the storage phosphor panel or screen is determined by the phosphor that is used, the amount of phosphor and the support.
- Higher absorption in the phosphor layer is advantageous for speed and image quality of the radiographic imaging system so there is a need to increase the thickness (the absorption) of the phosphor layer, this can only be done when the total absorption of phosphor layer and support remains almost constant.
- increasing the thickness of the phosphor layer must be compensated by lowering the absorption of penetrating radiation in the support.
- penetrating radiation of low energy e.g. mammography, certain non-destructive testing applications, etc.
- the contribution of the support to the absorption of the phosphor screen or panel or screen can not be neglected.
- the lowering of the absorption of penetrating radiation by the support can be done by lowering the thickness of the support, by using a support with low absorption, etc..
- the support of the storage phosphor panel or screen should have high mechanical strength, low brittleness and, in case of vacuum deposition of the phosphor on it, be able to withstand the temperatures encountered during vapour deposition.
- the support on which the phosphor is deposited can be heated up to a temperature of about 400°C. So use of a thermostable support is necessary. Therefore, though being a support containing only elements with low atomic number, a polymeric support is not the most suitable. It was now found that including an amorphous carbon film in the support did open perspectives in order to produce a binderless storage phosphor screen on a support with low X-ray absorption, even if the storage phosphor layer is applied by vacuum deposition at fairly high temperatures.
- Amorphous carbon films suitable for use in this invention are commercially available through, e.g., Tokay Carbon Co, LTD of Tokyo, Japan or Nisshinbo Industries, Inc of Tokyo, Japan, where they are termed "Glass-Like Carbon Film", or “Glassy Carbon”.
- the thickness of the amorphous carbon layer can range from 100 ⁇ m up to 3000 ⁇ m, a thickness between 500 ⁇ m and 2000 ⁇ m being preferred as compromise between flexibility, strength and X-ray absorption.
- a binderless storage phosphor screen the storage phosphor layer can be directly positioned adjacent to the amorphous carbon layer, e.g., by vacuum depositing the storage phosphor on the amorphous carbon film, and the screen can be used without adding further layers to the screen, this is a very simple embodiment of a storage phosphor screen of the present invention.
- This embodiment is shown in figure 1 wherein a storage phosphor layer (1) on a support (2) is adjacent to an amorphous carbon layer (23).
- an auxiliary layer can be added to the screen at the side of the amorphous carbon layer facing away from the phosphor layer.
- a screen is shown in figure 2 , wherein a phosphor layer (1) on a support (2) is schematically shown wherein the support includes an amorphous carbon layer (23) and an auxiliary layer (24).
- This auxiliary layer is preferably a polymeric layer that is laminated to the amorphous carbon layer.
- auxiliary layer laminated on the amorphous carbon layer.
- This auxiliary layer can be any polymeric film known in the art, e.g. polyester film, polyvinylchloride, polycarbonate, syntactic polystyrene, etc..
- Preferred polymeric films are polyester ester films, as e.g., polyethylene terephthalate films, polyethylene naphthalate films, etc..
- the thickness of the auxiliary layer (24) can range from 1 ⁇ m to 500 ⁇ m. It is possible to use a fairly thin amorphous carbon film, e.g., 400 ⁇ m and laminate a 500 ⁇ m thick auxiliary film to it as well as to use a thick amorphous carbon film, e.g., 2000 ⁇ m thick with a thin, e.g., 6 ⁇ m thick, polymeric film laminated onto it.
- the relative thickness of the amorphous carbon and polymeric film can be varied widely and is only directed by the required physical strength of the amorphous carbon during deposition of the phosphor layer and the required flexibility during use of the panel.
- the layer is a thin aluminum layer (thickness preferably lower than or equal to 10 ⁇ m, more preferably lower than or equal to 5 ⁇ m). Since such a thin metal layer can be quite corrosion sensitive it is preferred that, when a specularly reflecting metal layer is present in a panel or screen that this layer is covered with a barrier layer (a further auxiliary layer) that impedes water and/or moisture of reaching the relecting auxiliary layer.
- a barrier layer can be any moisture barrier layer known in the art, but is preferably a layer of parylene.
- Most preferred polymers for use in the barrier layer are vacuum deposited, preferably chemical vacuum deposited poly-p-xylylene film.
- a poly-p-xylylene has repeating units in the range from 10 to 10000, wherein each repeating unit has an aromatic nuclear group, whether or not substituted.
- the commercially available di-p-xylylene composition sold by the Union Carbide Co. under the trademark "PARYLENE” is thus preferred.
- compositions for the barrier layer are the unsubstituted "PARYLENE N", the monochlorine substituted "PARYLENE C”, the dichlorine substituted "PARYLENE D” and the “PARYLENE HT” (a completely fluorine substituted version of PARYLENE N, opposite to the other "parylenes” resistant to heat up to a temperature of 400°C and also resistant to ultra-violet radiation, moisture resistance being about the same as the moisture resistance of "PARYLENE C”).
- Most preferred polymers for use in the preparation of the barrier layer in a panel are poly(p-2-chloroxylylene), i.e. PARYLENE C film, poly(p-2,6-dichloroxylylene), i.e.
- PARYLENE D film and "PARYLENE HT" a completely fluorine substituted version of PARYLENE N.
- the advantage of parylene layers as moisture barrier layers in a panel or screen layer is the temperature resistance of the layers, the temperature resistance of the parylene layers is such that they can withstand the temperature need for vacuum depositing the storage phosphor.
- the use of parylene layers in storage phosphor screens has been disclosed in, e.g., EP-A's 1 286 362, 1 286 363, 1 286 364 and 1 286 365.
- a screen or a panel according to this third embodiment as set forth hereinbefore has ( Figure 3 ) a phosphor layer (1) and a support (2) wherein the support includes an amorphous carbon layer (23) and between the phosphor and the amorphous carbon layer a specularly reflecting layer (22) adjacent to the amorphous carbon layer and a parylene layer (21) on top of the reflecting layer.
- a polymeric layer (24) is laminated to the amorphous carbon layer.
- said reflective auxiliary layer (22) is an aluminum layer with a thickness between 0.2 ⁇ m and 200 ⁇ m.
- a method for producing a storage phosphor panel comprises the steps of :
- a method for producing a storage phosphor panel comprises the steps of :
- a method for producing a storage phosphor panel is comprising the steps of :
- the screen or panel can include on top of the phosphor layer any protective layer known in the art. Especially suitable for use are those protective layers disclosed in EP-A's 1 286 363, 1 316 969 and 1 316 970. Screens or panels wherein a moisture-repellent layer is present inbetween said substrate and said phosphor layer are advantageously used, and, furtheron a screen or panel wherein, adjacent to the said phosphor layer, a moisture-repellent layer is coated as an outermost layer is even more preferred. Especially said screens or panels having moisture-repellent parylene layers are recommended. Screens or panels, wherein said phosphor layer is sandwiched between two moisture-repellent parylene layers provide an excellent protection.
- the screen or the panel can also have reinforced edges as described in, e.g., US-A-5 334 842 and US-A-5 340 661 .
- the surface of the phosphor layer (1) in a panel or screen can be made smaller than the surface of the support (2) so that the phosphor layer does not reach the edges of the support.
- a screen has been disclosed in, e.g., EP-A 1 286 363 .
- the storage phosphor used in a panel or screen is preferably an alkali metal storage phosphor.
- a phosphor is disclosed in US-A-5 736 069 and corresponds to the formula : M 1+ X.aM 2+ X' 2 bM 3+ X'' 3 :cZ wherein: M 1+ is at least one member selected from the group consisting of Li, Na, K, Cs and Rb, M 2+ is at least one member selected from the group consisting of Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu, Pb and Ni, M 3+ is at least one member selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Bi, In and Ga, Z is at least one member selected from the group Ga 1+ , Ge 2+ , Sn 2+, Sb 3+ and As 3+ , X,
- An especially preferred phosphor for use in a panel or screen is a CsX:Eu stimulable phosphor, wherein X represents a halide selected from the group consisting of Br and Cl, produced by a method comprising the steps of :
- the phosphor is preferably vacuum deposited on the support under conditions disclosed in EP-A-1 113 458 and EP-A-1 118 540 .
- the panel or screen is a binderless phosphor panel or screen, wherein said phosphor layer comprises a needle-shaped CsX:Eu phosphor, wherein X represents a halide selected from the group consisting of Br and Cl.
- the present invention deals with a method for exposing an object to X-rays comprising the steps of :
- the present invention further includes a method according as described just hereinbefore, wherein said X-ray tube is equipped for emitting X-rays with an energy lower than or equal to 40 keV.
- the method is thus very well suited for use in mammography where X-ray machines with low keV are used, and in certain non-destructive testing applications.
- CsBr:Eu phosphor layers (of varying thicknesses, expressed in ⁇ m and indicated in the Table 1) were coated on varying supports (aluminum, a-C "amorphous carbon", glass and iron), having varying thicknesses (expressed in ⁇ m in the Table 1) and X-ray energies (doses in mR) reaching the "phototimer" have been summarised in the Table 1 for each examined panel or screen.
- a thickness of the support layer the thickness still offering enough dose at the position of the phototimer after the X-rays have passed the cassette, for differing thicknesses of the CsBr:Eu phosphor layer, have been given in the Table 1 hereinafter.
- amorphous carbon (a-C) support is superior as little absorption occurs, if compared e.g. with Fe (not suitable for use, even not for a layer thickness of only 100 ⁇ m) and with aluminum (suitable for use up to 800 ⁇ m for a thinner phosphor layer of 100 ⁇ m): amorphous carbon provides enough dose at the position of the phototimer, even for the thickest phosphor layer (150 ⁇ m) and a thickness of 2000 ⁇ m is perfectly suitable for use! Amorphous carbon is comparable with glass as illustrated in Table 1, but it is superior with respect to glass as it is much more suitable to be applied in the manufacturing of phosphor panels or screens.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Conversion Of X-Rays Into Visible Images (AREA)
Description
- This invention relates to a method for exposing an object to X-rays comprising the use of a binderless phosphor screen with a support including an amorphous carbon (a-C) layer.
- A well-known use of phosphors is in the production of X-ray images. In a conventional radiographic system an X-ray radiograph is obtained by X-rays transmitted image-wise through an object and converted into light of corresponding intensity in a so-called intensifying screen (X-ray conversion screen) wherein phosphor particles absorb the transmitted X-rays and convert them into visible light and/or ultraviolet radiation to which a photographic film is more sensitive than to the direct impact of X-rays.
- According to another method of recording and reproducing an X-ray pattern disclosed e.g., in
US-A-3 859 527 a special type of phosphor is used, known as a photostimulable phosphor, which being incorporated in a panel or screen, is exposed to incident pattern-wise modulated X-ray beam and, as a result thereof, temporarily stores energy contained in the X-ray radiation pattern. At some interval after the exposure, a beam of visible or infra-red light scans the panel or screen to stimulate the release of stored energy as light that is detected and converted to sequential electrical signals which can be processed to produce a visible image. For this purpose, the phosphor should store as much as possible of the incident X-ray energy and emit as little as possible of the stored energy until stimulated by the scanning beam. This is called "digital radiography" or "Computed Radiography" (CR). - In both kinds of radiography the amount of exposure given for an examination is often tuned by a "phototimer". A "phototimer" comprises a radiometer for measuring the radiation dose passing through the object (patient) and the radiographic imaging system and a connection to the source of penetrating radiation for switching the penetrating radiation source off as soon as a pre-set dose is reached. In systems using such a phototimer it is important that a well measurable dose reaches the radiometer in the phototimer, since when the dose reaching the phototimer is too low, the reproducibility of the off-switching of the source of penetrating radiation is not what it should be from the point of view of image quality. Thus, the imaging system should itself only absorb penetrating radiation up to such an extent as is necessary for good speed and image quality so that - with a patient dose as low as possible and only dictated by the examination at hand - the radiometer is reached by a sufficiently high exposure dose for reproducible off-switching of the source of penetrating radiation.
- In a practical setting the amount of radiation that reaches the "phototimer" is determined by the absorption of penetrating radiation by the object, the tube side of the cassette containing the storage phosphor panel or screen and the back side of the cassette. The absorption of the storage phosphor panel or screen is determined by the phosphor that is used, the amount of phosphor and the support. Higher absorption in the phosphor layer is advantageous for speed and image quality of the radiographic imaging system so there is a need to increase the thickness (the absorption) of the phosphor layer, this can only be done when the total absorption of phosphor layer and support remains almost constant. Thus increasing the thickness of the phosphor layer must be compensated by lowering the absorption of penetrating radiation in the support. Especially in radiographic techniques where penetrating radiation of low energy is used (e.g. mammography, certain non-destructive testing applications, etc.) the contribution of the support to the absorption of the phosphor screen or panel or screen can not be neglected.
- The lowering of the absorption of penetrating radiation by the support can be done by lowering the thickness of the support, by using a support with low absorption, etc.. On the other hand the support of the storage phosphor panel or screen should have high mechanical strength, low brittleness and, in case of vacuum deposition of the phosphor on it, be able to withstand the temperatures encountered during vapour deposition. Thus the need for a support giving a good compromise between often contradictory properties, as those cited above, remains present.
- It is an object of the invention to provide a method for exposing an object to X-rays comprising the steps of :
- providing an X-ray machine including an X-ray tube equipped for emitting X-rays with an energy lower than or equal to 70 keV.
- and a phototimer coupled to said X-ray tube for switching said tube on and off in accordance with an X-ray dose reaching said phototimer,
- placing an object between said X-ray tube and said phototimer,
- placing a binderless storage phosphor panel or screen between said object and said phototimer and
- activating said X-ray tube for exposing said object, said panel or screen and said phototimer until said phototimer switches said X-ray tube off,
- wherein said binderless storage phosphor panel or screen comprises a vacuum deposited phosphor layer (1) on a support (2), and wherein said support includes a layer of amorphous carbon (23).
- Further advantages and embodiments of the present invention will become apparent from the following description.
-
-
Figure 1 shows schematically an embodiment of a storage phosphor panel or screen. -
Figure 2 shows schematically a further embodiment of a storage phosphor panel or screen. -
Figure 3 shows schematically an other embodiment of a storage phosphor panel or screen. - In the production of binderless phosphor screens by means of chemical vapour deposition in vacuum, the support on which the phosphor is deposited can be heated up to a temperature of about 400°C. So use of a thermostable support is necessary. Therefore, though being a support containing only elements with low atomic number, a polymeric support is not the most suitable. It was now found that including an amorphous carbon film in the support did open perspectives in order to produce a binderless storage phosphor screen on a support with low X-ray absorption, even if the storage phosphor layer is applied by vacuum deposition at fairly high temperatures. Amorphous carbon films suitable for use in this invention are commercially available through, e.g., Tokay Carbon Co, LTD of Tokyo, Japan or Nisshinbo Industries, Inc of Tokyo, Japan, where they are termed "Glass-Like Carbon Film", or "Glassy Carbon".
- In a binderless phosphor panel or screen the thickness of the amorphous carbon layer can range from 100 µm up to 3000 µm, a thickness between 500 µm and 2000 µm being preferred as compromise between flexibility, strength and X-ray absorption.
- In a binderless storage phosphor screen the storage phosphor layer can be directly positioned adjacent to the amorphous carbon layer, e.g., by vacuum depositing the storage phosphor on the amorphous carbon film, and the screen can be used without adding further layers to the screen, this is a very simple embodiment of a storage phosphor screen of the present invention. This embodiment is shown in
figure 1 wherein a storage phosphor layer (1) on a support (2) is adjacent to an amorphous carbon layer (23). - In a further embodiment of the storage phosphor screen or panel an auxiliary layer can be added to the screen at the side of the amorphous carbon layer facing away from the phosphor layer. Such a screen is shown in
figure 2 , wherein a phosphor layer (1) on a support (2) is schematically shown wherein the support includes an amorphous carbon layer (23) and an auxiliary layer (24). This auxiliary layer is preferably a polymeric layer that is laminated to the amorphous carbon layer. By doing so the mechanical strength, especially with respect to brittleness and flexibility, of the panel or screen is enhanced. The need for very high mechanical strength is especially present in the radiographic systems making use of a storage phosphor panel wherein during reading of the energy stored in the panel, the panel is automatically removed from the cassette, moved through a reader, often via a sinuous path, and then put back in the cassette. In such a reader it is quite advantageous to make use of a screen or panel with an auxiliary layer laminated on the amorphous carbon layer. This auxiliary layer can be any polymeric film known in the art, e.g. polyester film, polyvinylchloride, polycarbonate, syntactic polystyrene, etc.. Preferred polymeric films are polyester ester films, as e.g., polyethylene terephthalate films, polyethylene naphthalate films, etc.. The thickness of the auxiliary layer (24) can range from 1 µm to 500 µm. It is possible to use a fairly thin amorphous carbon film, e.g., 400 µm and laminate a 500 µm thick auxiliary film to it as well as to use a thick amorphous carbon film, e.g., 2000 µm thick with a thin, e.g., 6 µm thick, polymeric film laminated onto it. The relative thickness of the amorphous carbon and polymeric film can be varied widely and is only directed by the required physical strength of the amorphous carbon during deposition of the phosphor layer and the required flexibility during use of the panel. - It has been shown, e.g. in the European Patent Application No.
02100763.8 - Thus a screen or a panel according to this third embodiment as set forth hereinbefore has (
Figure 3 ) a phosphor layer (1) and a support (2) wherein the support includes an amorphous carbon layer (23) and between the phosphor and the amorphous carbon layer a specularly reflecting layer (22) adjacent to the amorphous carbon layer and a parylene layer (21) on top of the reflecting layer. A polymeric layer (24) is laminated to the amorphous carbon layer. In a preferred embodiment said reflective auxiliary layer (22) is an aluminum layer with a thickness between 0.2 µm and 200 µm. - A method for producing a storage phosphor panel comprises the steps of :
- providing an amorphous carbon film,
- vacuum depositing a storage phosphor layer on said amorphous carbon film and
- optionally laminating a polymeric film on the side of the amorphous carbon film not covered by said phosphor.
- A method for producing a storage phosphor panel comprises the steps of :
- providing an amorphous carbon film
- applying a specularly reflecting layer on said amorphous carbon film,
- vacuum depositing a storage phosphor layer on said amorphous carbon film and
- optionally laminating a polymeric film on the side of the amorphous carbon film not covered by said phosphor.
- A method for producing a storage phosphor panel is comprising the steps of :
- providing an amorphous carbon film
- applying a specularly reflecting layer on said amorphous carbon film
- chemical vacuum depositing a parylene layer on top of said specularly reflecting layer,
- vacuum depositing a storage phosphor layer on said amorphous carbon film and, optionally,
- laminating a polymeric film on the side of the amorphous carbon film not covered by said phosphor.
- The screen or panel can include on top of the phosphor layer any protective layer known in the art. Especially suitable for use are those protective layers disclosed in EP-A's 1 286 363, 1 316 969 and 1 316 970. Screens or panels wherein a moisture-repellent layer is present inbetween said substrate and said phosphor layer are advantageously used, and, furtheron a screen or panel wherein, adjacent to the said phosphor layer, a moisture-repellent layer is coated as an outermost layer is even more preferred. Especially said screens or panels having moisture-repellent parylene layers are recommended. Screens or panels, wherein said phosphor layer is sandwiched between two moisture-repellent parylene layers provide an excellent protection.
- The screen or the panel can also have reinforced edges as described in, e.g.,
US-A-5 334 842 andUS-A-5 340 661 . - The surface of the phosphor layer (1) in a panel or screen can be made smaller than the surface of the support (2) so that the phosphor layer does not reach the edges of the support. Such a screen has been disclosed in, e.g.,
EP- .A 1 286 363 - The storage phosphor used in a panel or screen is preferably an alkali metal storage phosphor. Such a phosphor is disclosed in
US-A-5 736 069 and corresponds to the formula : M1+X.aM2+X'2bM3+X''3:cZ
wherein: M1+ is at least one member selected from the group consisting of Li, Na, K, Cs and Rb,
M2+ is at least one member selected from the group consisting of Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu, Pb and Ni,
M3+ is at least one member selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Bi, In and Ga,
Z is at least one member selected from the group Ga1+, Ge2+, Sn2+, Sb3+ and As3+,
X, X' and X'' can be the same or different and each represents a halogen atom selected from the group consisting of F, Br, Cl, I and 0 ≤ a ≤ 1, 0 ≤ b ≤ 1 and 0 ≤ c ≤ 0.2. - An especially preferred phosphor for use in a panel or screen is a CsX:Eu stimulable phosphor, wherein X represents a halide selected from the group consisting of Br and Cl, produced by a method comprising the steps of :
- mixing said CsX with between 10-3 and 5 mol % of a Europium compound selected from the group consisting of EuOX', EuX'2 and EuX'3, X' being a member selected from the group consisting of F, Cl, Br and I;
- firing said mixture at a temperature above 450 °C;
- cooling said mixture and
- recovering the CsX:Eu phosphor.
- Such a phosphor has been disclosed in
EP-A-1 203 394 . - The phosphor is preferably vacuum deposited on the support under conditions disclosed in
EP-A-1 113 458 andEP-A-1 118 540 . - In a preferred embodiment the panel or screen is a binderless phosphor panel or screen, wherein said phosphor layer comprises a needle-shaped CsX:Eu phosphor, wherein X represents a halide selected from the group consisting of Br and Cl.
- The present invention deals with a method for exposing an object to X-rays comprising the steps of :
- providing an X-ray machine including an X-ray tube equipped for emitting X-rays with an energy lower than or equal to 70 keV and a phototimer coupled to said X-ray tube for switching said tube on and off in accordance with an X-ray dose reaching said phototimer,
- placing an object between said X-ray tube and said phototimer
- placing a binderless storage phosphor panel or screen between said object and said phototimer and
- activating said X-ray tube for exposing said object, said cassette and said phototimer until said phototimer switches said X-ray tube off.
- The present invention further includes a method according as described just hereinbefore, wherein said X-ray tube is equipped for emitting X-rays with an energy lower than or equal to 40 keV.
- The method is thus very well suited for use in mammography where X-ray machines with low keV are used, and in certain non-destructive testing applications.
-
- 1. phosphor layer
- 2. support
- 21 auxiliary layer, moisture barrier layer
- 22 auxiliary layer, specularly reflecting layer
- 23 amorphous carbon layer
- 24 auxiliary layer, polymeric layer
- An X-ray cassette with a phosphor screen or panel was exposed with X-rays having an energy of 28 keV from a Mo-anode (30 µm Mo, intern filtering and without filtering,respectively).
- A Mammory Detail R® screen, trade marketed product from Agfa-Gevaert, Morstel, Belgium, was taken as a comparative screen: as that system just admits use of a "phototimer" (with respect to absorption of X-ray exposure energy as explained in the detailed description hereinbefore). Absorption for all examined cassettes with screens or panels should thus not exceed the absorption, measured for the comparative screen, set forth hereinbefore.
- Starting from a 10 mR X-ray dose reaching the cassette, X-rays passing through 4 cm of a polymethyl methacrylate polymeric layer, further consecutively passing the cassette bottom (3 mm of polyethylene), the panel or screen (varying composition in the experiments as will be explained hereinafter) and the cassette cover (4.1 mm of polyethylene), it has been measured that a dose in the range from 0.75 up to 0.85 mR is required in order to get an acceptable and precise working of the "phototimer", in order to avoid too much exposure to X-rays for the patient.
- In the panels or screens, CsBr:Eu phosphor layers (of varying thicknesses, expressed in µm and indicated in the Table 1) were coated on varying supports (aluminum, a-C "amorphous carbon", glass and iron), having varying thicknesses (expressed in µm in the Table 1) and X-ray energies (doses in mR) reaching the "phototimer" have been summarised in the Table 1 for each examined panel or screen. As a thickness of the support layer, the thickness still offering enough dose at the position of the phototimer after the X-rays have passed the cassette, for differing thicknesses of the CsBr:Eu phosphor layer, have been given in the Table 1 hereinafter.
Table 1 Support material and its thickness (µm) CsBr:Eu phosphor layer thickness (µm) Dose detected at the phototimer (mR) Al 100 µm 150 µm 0.75 Al 400 µm 125 µm 0.78 Al 800 µm 100 µm 0.76 a-C 2000 µm 150 µm 0.73 a-C 2000 µm 125 µm 0.81 a-C 2000 µm 100 µm 0.91 Glass 2000 µm 140 µm 0.95 Glass 2000 µm 150 µm 0.85 Glass 2000 µm 160 µm 0.76 Fe 100 µm 60 µm 0.55 Fe 100 µm 80 µm 0.44 Fe 100 µm 100 µm 0.36 - From the results obtained in the Table 1, it is clear that the amorphous carbon (a-C) support is superior as little absorption occurs, if compared e.g. with Fe (not suitable for use, even not for a layer thickness of only 100 µm) and with aluminum (suitable for use up to 800 µm for a thinner phosphor layer of 100 µm): amorphous carbon provides enough dose at the position of the phototimer, even for the thickest phosphor layer (150 µm) and a thickness of 2000 µm is perfectly suitable for use! Amorphous carbon is comparable with glass as illustrated in Table 1, but it is superior with respect to glass as it is much more suitable to be applied in the manufacturing of phosphor panels or screens.
Claims (8)
- A method for exposing an object to X-rays comprising the steps of :- providing an X-ray machine including an X-ray tube equipped for emitting X-rays with an energy lower than or equal to 70 keV.- and a phototimer coupled to said X-ray tube for switching said tube on and off in accordance with an X-ray dose reaching said phototimer,- placing an object between said X-ray tube and said phototimer,- placing a binderless storage phosphor panel or screen between said object and said phototimer and- activating said X-ray tube for exposing said object, said panel or screen and said phototimer until said phototimer switches said X-ray tube off,- wherein said binderless storage phosphor panel or screen comprises a vacuum deposited phosphor layer (1) on a support (2), and wherein said support includes a layer of amorphous carbon (23).
- Method according to claim 1, wherein the X-ray tube is equipped for emitting X-rays with an energy lower than or equal to 40 keV.
- Method according to claim 1, wherein said panel or screen comprises a support including a layer of amorphous carbon having a thickness between 500 µm and 2000 µm.
- Method according to claim 1, wherein said panel or screen is comprised in a cassette.
- Method according to claim 1, wherein the dose reaching the phototimer is in the range from 0.75 up to 0.85 mR.
- Method according to any of the preceding claims, wherein said phosphor layer comprises a needle shaped CsX:Eu phosphor, wherein X represents a halide selected from the group consisting of Br and Cl.
- Method according to any of the preceding claims, wherein said method is a mammographic application method.
- Method according to any of the preceding claims, wherein said support further includes a reflective auxiliary aluminum layer (22) with a thickness between 0.2 µm and 200 µm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20030101862 EP1376616B1 (en) | 2002-06-28 | 2003-06-25 | Method for producing X-ray images using a binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02100764 | 2002-06-28 | ||
EP02100764 | 2002-06-28 | ||
EP20030101862 EP1376616B1 (en) | 2002-06-28 | 2003-06-25 | Method for producing X-ray images using a binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1376616A2 EP1376616A2 (en) | 2004-01-02 |
EP1376616A3 EP1376616A3 (en) | 2007-08-08 |
EP1376616B1 true EP1376616B1 (en) | 2012-08-15 |
Family
ID=29718296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20030101862 Expired - Lifetime EP1376616B1 (en) | 2002-06-28 | 2003-06-25 | Method for producing X-ray images using a binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP1376616B1 (en) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5466947A (en) * | 1994-03-18 | 1995-11-14 | Bio-Rad Laboratories, Inc. | Protective overlayer for phosphor imaging screen |
EP0751200B1 (en) * | 1995-06-30 | 1999-03-03 | Agfa-Gevaert N.V. | A radiation image storage screen comprising an alkali metal halide phosphor |
JP4279462B2 (en) * | 1998-06-18 | 2009-06-17 | 浜松ホトニクス株式会社 | Scintillator panel, radiation image sensor and manufacturing method thereof |
WO1999066349A1 (en) * | 1998-06-18 | 1999-12-23 | Hamamatsu Photonics K.K. | Scintillator panel, radiation image sensor, and method for manufacturing the same |
EP1113458B1 (en) * | 1999-12-27 | 2005-02-02 | Agfa-Gevaert | A binderless storage phosphor screen with needle shaped crystals and methods for producing the same |
DE10036209C1 (en) * | 2000-07-25 | 2002-02-07 | Siemens Ag | X-ray image amplifier for providing high intensity visible image has aluminum (alloy) carrier provided with intermetallic compound coating layer and X-ray luminescent layer |
US6835936B2 (en) * | 2001-02-07 | 2004-12-28 | Canon Kabushiki Kaisha | Scintillator panel, method of manufacturing scintillator panel, radiation detection device, and radiation detection system |
EP1318525A3 (en) * | 2001-12-05 | 2007-03-28 | Agfa-Gevaert | Radiation image storage panel |
-
2003
- 2003-06-25 EP EP20030101862 patent/EP1376616B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP1376616A3 (en) | 2007-08-08 |
EP1376616A2 (en) | 2004-01-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7368746B2 (en) | Phosphor panel | |
EP0393662B1 (en) | Radiation image storage panel, radiographic intersifying screen and processes for the preparation of the same | |
US7211809B2 (en) | Radiographic image conversion panel | |
US7102143B2 (en) | Binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer | |
US5378897A (en) | Radiation image storage panel | |
EP0508416B1 (en) | Radiation image storage panel | |
US7196341B2 (en) | Binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer | |
US6992304B2 (en) | Radiation image storage panel | |
US7091510B2 (en) | Method for storing and reproducing radiation image and radiation image storage device | |
EP1376616B1 (en) | Method for producing X-ray images using a binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer | |
JP2004085367A (en) | Radiation image conversion panel | |
EP1492127A1 (en) | A binderless storage phosphor screen comprising a support including an amorphous (a-C) carbon layer | |
JP4323243B2 (en) | Radiation image conversion panel | |
US20040026632A1 (en) | Stimulable phosphor screen showing less scattering upon stimulation | |
JP2004251882A (en) | Storage phosphor screen using no bonding agent equipped with support containing amorphous carbon layer | |
US20040001953A1 (en) | Method for manufacturing a transparent binderless storage phosphor screen | |
EP1376614A2 (en) | Method for manufacturing a transparent binderless storage phosphor screen | |
JP2640021B2 (en) | Radiation image conversion panel and radiation image reproduction method | |
JP2597515B2 (en) | Manufacturing method of radiation image conversion panel | |
EP1808865A1 (en) | Radiation image converting panel and method for manufacture thereof | |
US7173258B2 (en) | Radiation image conversion panel and preparation method thereof | |
JP2549913B2 (en) | Radiation image conversion panel | |
US7235279B2 (en) | Process for producing a radiation image storage panel | |
JP2549912B2 (en) | Manufacturing method of radiation image conversion panel | |
JP2002071899A (en) | Moisture-proof protective film for radioactive image conversion panel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: AGFA HEALTHCARE NV |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
17P | Request for examination filed |
Effective date: 20080208 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: AGFA HEALTHCARE NV |
|
17Q | First examination report despatched |
Effective date: 20080717 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RTI1 | Title (correction) |
Free format text: METHOD FOR PRODUCING X-RAY IMAGES USING A BINDERLESS STORAGE PHOSPHOR SCREEN COMPRISING A SUPPORT INCLUDING AN AMORPHOUS (A-C) CARBON LAYER |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: TOSHIO, TAKABAYASHI C/O HAMAMATSU PHOTONICS K.K. Inventor name: LEBLANS, PAUL AGFA-GEVAERT, |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 60341811 Country of ref document: DE Effective date: 20121011 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20130516 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20130522 Year of fee payment: 11 Ref country code: GB Payment date: 20130620 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20130617 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 60341811 Country of ref document: DE Effective date: 20130516 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60341811 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20140625 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60341811 Country of ref document: DE Effective date: 20150101 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150227 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140625 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 |