EP1512154B1 - Matiere de protection contre les rayonnements, procede de production d'une matiere de protection contre les rayonnements et utilisation de cette matiere - Google Patents

Matiere de protection contre les rayonnements, procede de production d'une matiere de protection contre les rayonnements et utilisation de cette matiere Download PDF

Info

Publication number
EP1512154B1
EP1512154B1 EP20030787749 EP03787749A EP1512154B1 EP 1512154 B1 EP1512154 B1 EP 1512154B1 EP 20030787749 EP20030787749 EP 20030787749 EP 03787749 A EP03787749 A EP 03787749A EP 1512154 B1 EP1512154 B1 EP 1512154B1
Authority
EP
European Patent Office
Prior art keywords
radiation
weight
radiation protection
material according
protection material
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
Application number
EP20030787749
Other languages
German (de)
English (en)
Other versions
EP1512154A1 (fr
Inventor
Axel Thiess
Clemens Reizel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Paul Hartmann AG
Original Assignee
Paul Hartmann AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Paul Hartmann AG filed Critical Paul Hartmann AG
Publication of EP1512154A1 publication Critical patent/EP1512154A1/fr
Application granted granted Critical
Publication of EP1512154B1 publication Critical patent/EP1512154B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/10—Organic substances; Dispersions in organic carriers
    • G21F1/103—Dispersions in organic carriers
    • G21F1/106—Dispersions in organic carriers metallic dispersions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y10T428/257—Iron oxide or aluminum oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers

Definitions

  • the invention relates to a radiation protection material for the shielding of X-rays and / or gamma rays from a film-like, multilayer coating material in which radiation-absorbing particles are dispersed.
  • an energy absorbing material comprising a layer consisting of a polymer composition comprising 7 to 30% by weight of a specific polar thermoplastic polymer, 0 to 15% by weight of plasticizer and 70 to 93% by weight of an inorganic composition.
  • the inorganic composition consists of at least two elements, which should protect against radiation in a way that is better than lead.
  • EP 0 372 758 A1 a material consisting of 4 to 19% by weight of a polar thermoplastic polymer, 0 to 10% by weight of a plasticizer and 81 to 96% by weight of an inorganic compound.
  • DE 199 55 192 A1 discloses a method for producing a radiation protection material in which a thermoplastic, vulcanizable elastomer to which a metal powder is added is used.
  • Another radiation protection material describes the U.S. Patent 5,908,884 in which a high-absorptivity material for radiation is embedded in a vulcanized fluororubber material.
  • PVC plastisol materials are from the documents US 3,061,491 such as US 3,200,085 previously known.
  • the invention has for its object to provide a radiation protection material, which with a low weight and high flexibility of the material a high Radiation protection effect over a wide application or energy range allows.
  • the invention solves this object by a radiation protection material for the shielding of X-rays and gamma rays from a film-like multilayer coating material in which radiation-absorbing particles are dispersed, with the features of claim 1 and by a method according to claim 15 and a use according to claim 16
  • the layer material consists of at least one support layer and at least one radiation-absorbing layer, wherein the radiation-absorbing layer comprises a curable polymer preparation which is flowable in the processing state and wherein the effective lead content ⁇ 15 wt .-% is.
  • a material is provided whose radiation-absorbing layer in the state to be applied to the support layer is flowable, that is, either liquid or syrupy viscous and in particular in the range of 20,000 - 100,000 mPa s.
  • the fluidity should preferably be below 80 ° C, especially at room temperature. At temperatures above 80 ° C, curing of the polymer preparation may occur.
  • the curable polymer preparation comprises a PVC plastisol. This is flowable at room temperature. Furthermore, the polymer preparation comprises a liquid synthetic rubber. Such a preparation makes it possible to plasticize and vulcanize the liquid, crosslinkable and vulcanizable polymer matrix in one step and to harden it as a result. After hardening, a three-dimensional wide-mesh plastic structure with rubber-elastic behavior forms.
  • Liquid synthetic rubber is a group of specialty rubbers. It has a lower viscosity than the conventional rubbers, which are uncrosslinked, but crosslinkable (vulcanizable) polymers with rubber-elastic properties at room temperature. At higher temperatures and under the influence of deforming forces, rubbers also show viscous flow and can therefore also be shaped using appropriate conditions.
  • liquid rubbers make it easier to incorporate additives such as vulcanization accelerators, fillers, plasticizers or activators and are based on silicone, polyurethane, polyesters, polyethers and diene rubbers. With liquid silicone rubbers, the "cold-curing" one-component types RTV dominate.
  • Liquid polyurethane rubbers usually consist of polyurethane with isocyanate end groups and are usually vulcanized with weakly basic di- and polyamines.
  • Liquid diene rubbers are predominantly prepared by anionic polymerization of dienes with bifunctional starters. The resulting macro-dianions are reacted with carbon dioxide, ethylene oxide or ethylene sulfide to give polymers with carboxy, hydroxy or sulfhydryl end groups.
  • the vulcanization then takes place by reaction of these end groups with, for example, polyfunctional isocyanates.
  • concentration of crosslinkers must be relatively high because of the low molecular weights of the liquid rubbers. While the properties of the resulting elastomers in the liquid rubbers based on polyurethane similar to those of regular. Polyurethanes, vulcanizates of liquid diene rubbers have far lower tear strengths and elongation at break than vulcanizates of regular diene rubbers.
  • the plastisols which can be used according to the invention are a dispersion of plastics, in particular of by emulsion or microemulsion polymerization polyvinyl chloride, in high-boiling organic solvents which act as a plasticizer at higher temperatures for a polymer. Upon heating, the solvents diffuse into the dispersed plastic particles, intercalating there between the macromolecules, thereby plasticizing the plastics. Upon cooling, the materials treated in this way gel into flexible, dimensionally stable and abrasion-resistant systems whose properties can be influenced by added auxiliaries, such as pigments or stabilizers.
  • auxiliaries such as pigments or stabilizers.
  • plasticizable polymers or copolymers or block polymers or polymer blends dissolved or mixed in one or more plasticizers, for example PVC plastisol, polyolefin plastisol and LDPE plastisol or HDPE plastisol and polymethacrylate plastisol or mixtures thereof may be used.
  • plasticizers for example PVC plastisol, polyolefin plastisol and LDPE plastisol or HDPE plastisol and polymethacrylate plastisol or mixtures thereof may be used.
  • synthetic rubbers all liquid rubbers such as polyurethane rubbers, silicone rubbers and other synthetic rubbers, based on polyesters, polyethers or dienes, which are flowable or liquid up to a temperature of 80 ° C, such as acrylonitrile-butadiene synthetic rubbers are used.
  • a composition may be provided in which the polymer preparation contains between 20 and 40 wt .-% PVC and between 10 and 35 wt .-% of the liquid synthetic rubber, in particular an acrylonitrile-butadiene polymer and additives between 0 and 10 wt. -% such as stabilizers, anti-aging agents, starters and accelerators and residual plasticizers.
  • the proportion of PVC is between 25 and 35 wt .-% and in particular between 29 and 32 wt .-%.
  • the liquid rubber can be provided in particular be that between 15 and 25 wt .-% and in particular between 17 and 23 wt .-% of liquid rubber, in particular acrylonitrile-butadiene polymer is provided.
  • the effective lead content is ⁇ 10% by weight, in particular ⁇ 5% by weight and in particular ⁇ 1% by weight and in particular 0% by weight, ie it is therefore a completely lead-free material where the toxic substance lead is no longer present.
  • the specific lead equivalent of the material is ⁇ 30, in particular ⁇ 32 and preferably ⁇ 35 at a tube voltage in the range of 60 to 125 kV.
  • the lead equivalent value of the material as a specific lead equivalent value ⁇ 30 at at least two measuring points at least 20 kV apart in a tube voltage range between 60 - 125 kV according to IEC 1331-1 / EN 61331, in particular at three or more points apart where the furthest apart points are for example 40 kV, in particular 45 kV and particularly preferably 65 kV apart.
  • a measurement is carried out at, for example, 60 kV, 80 kV and 100 kV and 125 kV, and at all of these measuring points and in particular also in the areas between, the specific lead equivalent is ⁇ 30, in particular ⁇ 32 and in particular ⁇ 34.
  • the determination of the lead equivalent or lead equivalent is carried out according to the specified standard on a difference measurement, that is, the amount of radiation is incident on a detector, once as empty measurement and once with a radiation-absorbing material and from the difference of these values, the transmitted radiation is determined directly ,
  • the test setup is to be taken from IEC 1331-1 / EN 61331.
  • the amount of transmitted radiation is used to determine the lead equivalent.
  • the radiation source is an X-ray tube with a standard tungsten anode. This tube is operated at 300 - 500 mA.
  • the emission of the radiation is metered in the range of 10 - 100 ms.
  • the radiation quality reflects the radiation of the radiation used in the medical field. For illustration, the value as a specific lead equivalent value was referred to leadless, with the inaccuracy being +/- 1.
  • the carrier layer also consists of PVC plastisol material and / or polyurethane and / or polyester and / or polyolefins and / or silicone rubbers and / or the polymer preparation of the radiation-absorbing layer.
  • radiation-absorbing particles which realize a radiation-absorbing effect of the carrier layer can also be introduced into the carrier layer.
  • the combination of one or more carrier layers and one or more radiation protection layers can produce a material which is extremely flexible and thin, in particular lead-free and a foil-like design having.
  • the sequence of layers is freely selectable.
  • the layers can be made of different materials and have different properties. In this way, the material is particularly suitable for textile applications. Due to the high flexibility and low weight, a wearer is not hindered in their activity, while a high radiation protection effect is achieved by the high specific lead equivalent at the same time.
  • the carrier layer serves in particular to give strength.
  • the proportion of the polymer preparation to the radiation-absorbing layer less than 20 wt .-%, but more than 0 wt .-% and the proportion of the radiation-absorbing particles is more than 80 wt .-%.
  • the polymer preparation on the radiation-absorbing layer can be between 5 and 20% by weight and in particular between 10 and 20% by weight.
  • the proportion of the radiation-absorbing particles may in particular be between 80 and 95% by weight and in particular between 80 and 90% by weight. In this case, the amount of polymer preparation must be sufficient to securely connect the particles introduced therein.
  • the radiation-absorbing particles comprise tin, bismuth, barium and / or tungsten. It can be selected from the metal itself, metal oxides or metal salts.
  • the effective amount of the radiation-absorbing particles in the radiation-absorbing layer should in particular 55-75 wt .-% tin powder, between 0 and 30 wt .-% bismuth, 0 - 10 wt .-% barium and / or 0 - 20 wt .-% Tungsten, the sum in each case 100 wt .-% results.
  • lead components are included, pure lead as well as lead oxide and lead salts can be provided here.
  • the tin powder consists of a mixture of two tin powders of different particle size distributions with approximately equal weight ratios.
  • the bismuth oxide powder that can be used has a D 50 value in the range of 4-100 ⁇ m.
  • the multilayer coating material preferably has a weight per unit area of 1.2 to 1.5 kg / m 2 , with a value of approximately 1.35 kg / m 2 being particularly desired.
  • the multilayered layer material in particular has a film thickness of 0.3 to 1.2 mm, in particular of 0.3 to 0.5 mm, preferably 0.35 to 0.45 mm.
  • the radiation protection material may be designed so that the carrier layer on its side facing away from the radiation-absorbing layer washable or abrasion resistant and / or solid to alcohols and / or disinfectants or has textile properties, for example, a flock is provided, the pleasant tactile properties when wearing ensures a product made of the material.
  • abrasion resistance may be provided to extend the shelf life of a product made from the material, as well as washability, especially in the medical field to be able to easily clean manufactured objects after use.
  • the material is very flexible.
  • the bending stiffness which is a measure of the flexibility of the material was determined according to DIN 53121 and compared for comparison with the bending stiffness of other lead-free radiation protection films.
  • the width-related bending stiffness measurement of the lead-free materials in the three-point method was carried out according to the beam method, wherein the test is carried out on a Zwick testing machine.
  • the method is used to produce a radiation protection material of the type described above.
  • the liquid phases are mixed before addition of the radiation-absorbing particles.
  • the overall material for the radiation absorbing layer may be processed so that the particles are homogeneously distributed and then degassed prior to painting, pouring, knife coating and / or applying to the backing layer.
  • the radiation-absorbing layer is subjected to ultrasound after it has been applied to the carrier layer.
  • the carrier layer is not only adhesively bonded to the radiation-absorbing layer, but is integrally connected to the radiation-absorbing layer by crosslinking the two layers together during application and curing of the radiation-absorbing layer on the carrier layer.
  • a physical anchor formation of the layers takes place with each other. This is done, for example, when using a PVC plastisol in the radiation-absorbing layer, provided that the material of the carrier layer is chosen so that the PVC plastisol can dissolve it.
  • the invention comprises a use of the radiation protection material described above as Radiation protection clothing, in particular as a radiation protection apron or radiation protection apron or sheath or flexible barriers, such as covers or curtains.
  • a radiation protection material can be easily produced, whereby a uniform, rapid and homogeneous distribution of the metal particles can be ensured in the polymer matrix, since a uniform distribution in a liquid polymer matrix is easy to implement and cumbersome kneading or walking as in the conventional radiation protection film materials can be omitted.
  • the resulting radiation protection material of several layers is very flexible and uniformly radiation-absorbing over a wide energy range.
  • FIG. 1 shows a cross-section through the lead-free foil-like radiation protection material, which is applied to a silicone-coated release paper 4.
  • the release paper 4 can be structured to produce a structure, for example a leather grain, on a carrier layer 2.
  • the carrier layer 2 of a PVC plastisol film is by knife coating on a silicone-coated release paper 4 and through subsequent gelling at 190-200 ° C formed.
  • the carrier layer 2 gives the radiation protection material sufficient strength.
  • a paste of the radiation-absorbing layer 3 is doctored onto this carrier layer 2 with a weight per unit area of 70-80 g / m 3 and then crosslinked or vulcanized in the drying oven at about 200 °.
  • the total thickness of the film-like layer material is then about 0.35-0.45 mm and has a total basis weight of about 1.35 kg / m 2 .
  • the paste from which the radiation-absorbing layer is formed consists of a PVC plastisol and a solvent-free and water-free acrylonitrile-butadiene liquid rubber and the metallic additives of tin powder and bismuth oxide powder.
  • the polymer mixture of the radiation absorbing layer 3 has 13 parts by weight of polymer material, 65 parts by weight of tin powder and 22 parts by weight of bismuth powder.
  • the tin powder consists of two different types with different grain size distribution (product name: TEGO-Zinngr imagine, TEGO 30 BG, TEGO 60 BG - Fa. Ecka Granules).
  • the tin powders with different particle size distribution are mixed in a ratio of 1: 1.
  • the bismuth oxide powder is also referred to in the nomenclature as yellow bismuth (Bi 2 O 3 ).
  • the D 50 value is a maximum of 10 ⁇ m with a typical value of 5.5 ⁇ m.
  • the lead-free radiation protection material may initially remain on the silicone-coated release paper layer 4 until it is made up into a radiation protection apron, for example.
  • polymer mixture 13% by weight Tin powder TEGO 60 BG (metallic) 35% by weight Tin powder TEGO 30 BG (metallic) 30% by weight Bismuth trioxide (Bi 2 O 3 ) 22% by weight
  • a polymer blend is given below. Parts by weight [g] DINP (plasticizer) 3400 TXIB (plasticizer) 600 Tin oxide (ZnO) 100 Sulfur (S) 100 Vulkazit D (vulcanization accelerator) 60 Vulkazit M (vulcanization accelerator) 60 Vestolit 1415 K 80 (PVC) 2800 Tegoprene (dispersing agent / anti-tack) 200 Nipol 1312 LV (liquid rubber) 1600 Total 8820
  • This polymer mixture enters the initially pasty radiation-absorbing layer at a weight fraction of about 13% by weight.
  • the proportion of PVC is about 31 wt .-%, the proportion of liquid rubber about 18 wt .-% and the amount of plasticizer about 45 wt .-% of the polymer composition.
  • the carrier layer 2 has the following composition: PVC 40-70% by weight Plasticizer (DINP) 30-50% by weight Aggregates for aging protection, ozone resistance, color pigments 0.1-0.5% by weight
  • the viscosity can be adjusted by changing the proportion of the plasticizer TXIB.
  • the radiation protection material described does not show a collapse of the shielding efficiency at tube voltage over 100 kV, but is within a voltage range of 60-150 kV within the prescribed tolerance limits of the international standard IEC 1331-1 / EN 61331.
  • the second figure now shows a table in which the sample number, the recipe number, the basis weight, the bending stiffness, the material thickness and then the shielding effects at a given x-ray tube voltage for 60 kV, 80 kV, 100 kV and 125 kV respectively for the specific as well the general lead equivalent.
  • the sample numbers 1-14 relate to radiation protection materials according to the invention. Sample Nos. 15 - 19 Xenolite lead-free and Suprasine are marketed products for lead-free radiation protection materials.
  • the specific lead equivalent of the x-ray tube voltage is defined as the lead equivalent at x-ray tube voltage x 100 / material thickness.
  • the lead equivalent was determined according to IEC 1331-1 / EN 61331.
  • compositions for the radiation protection layer are as follows: Recipe 1: 13% by weight of polymer preparation, 65% by weight of tin powder, 22% by weight of bismuth trioxide. Recipe 2: 11% by weight of polymer preparation, 62-66% by weight of tin powder, 27-23% by weight of bismuth powder. Recipe 3: 10-11% by weight of polymer preparation, 60-64% by weight of tin powder, 18-20% by weight of bismuth powder, 8-10% by weight of tungsten powder. Recipe 4: 12% by weight of polymer preparation, 65% by weight of tin powder, 10% by weight of barium fluoride, 13% by weight of tungsten powder.
  • composition of the polymer preparation is as follows in the formulations 1 - 4: composition Wt .-% Di-isononyl phthalate (DINP) - Vestolit 38 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) - Kran Chemie 6 Zinc oxide active - Rheinchemie Rheinau GmbH 1 Grinding sulfur - Solveig 1 N, N'-diphenylguanidine (Vulkacit D) - Rheinchemie Rheinau GmbH 0.5 2-mercaptobenzothiazole (MBT, Vulkacit Merkapto) - Rheinchemie Rheinau GmbH 0.5 PVC (Vestolit P 1415 K 80) - Vestolit 31 Ba / Zn stabilizer for PVC (Mark BZ 505) - Compton Vinyl Additive GmbH 1 Vulkanox DDA, (anti-aging agent) - Rheinchemie Rheinau GmbH 1 Acrylonitrile-butadiene polymer (Nipol 1312 LV
  • the samples made, in particular according to formulation 2 have a particularly good specific lead equivalent, in comparison with the known products, in particular via a Tube voltage range of at least 20 kV difference, where the absolute voltage values are between 60 and 125 kV.
  • the thickness of the xenolite material is 0.6 mm and this results in a bending stiffness for the material of 1.28 cN.
  • Suprasine needs a thickness of 0.65 mm to achieve this shielding performance and then has a flexural stiffness of 1.11 cN.
  • the composition according to the invention for example according to recipe 2, only needs a thickness of 0.45 mm to achieve this shielding value and achieves a bending stiffness of 0.43 cN. In this way, particularly light and flexible, comfortable for the wearer materials, especially for the production of textiles, such as clothing and barriers, created.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Inorganic Insulating Materials (AREA)
  • Sealing Material Composition (AREA)

Claims (16)

  1. Matériau de protection contre les rayonnements utilisé comme écran pour empêcher le passage des rayons X et/ou gamma, constitué d'un stratifié multicouches de type film dans lequel sont dispersées des particules absorbant les rayonnements, le stratifié étant constitué d'au moins une couche de support et une couche absorbant les rayonnements, la couche absorbant les rayonnements comprenant une préparation polymère durcissable qui est relativement fluide pour couler lorsqu'elle se trouve dans un état lui permettant d'être travaillée et la proportion de plomb active étant ≤ 15 % en poids, caractérisé en ce que la préparation polymère de la couche absorbant les rayonnements comprend un plastisol PVC ainsi qu'un composant caoutchouc liquide, en particulier un mélange de plastisol PVC et d'un composant caoutchouc liquide.
  2. Matériau de protection contre les rayonnements selon la revendication 1, caractérisé en ce que le matériau polymère comprend un fluidifiant et/ou des agents de réticulation et/ou d'autres produits auxiliaires.
  3. Matériau de protection contre les rayonnements selon la revendication 1 ou 2, caractérisé en ce que la préparation polymère contient entre 20 et 40 % en poids de PVC, entre 10 et 35 % en poids de caoutchouc liquide, entre 0 et 10 % en poids d'adjuvants et de produits auxiliaires, le reste étant composé d'un fluidifiant.
  4. Matériau de protection contre les rayonnements selon la revendication 3, caractérisé en ce que la préparation polymère contient entre 25 et 35 % en poids, en particulier 30 % en poids de PVC, entre 15 et 25 % en poids, en particulier 20 % en poids de caoutchouc liquide, entre 0 et 7 % en poids d'adjuvants et de produits auxiliaires, le reste étant composé d'un fluidifiant.
  5. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que la proportion de plomb active est ≤ 10 % en poids, en particulier ≤ 5 % en poids et en particulier est égale à 0 % en poids.
  6. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que l'équivalent plomb spécifique est ≥ 30, en particulier ≥ 32 et en particulier ≥ 34 pour au moins une tension de tube comprise dans une plage allant de 60 à 125 kV conformément à IEC 1331-1/EN 61331.
  7. Matériau de protection contre les rayonnements selon la revendication 6, caractérisé en ce que l'équivalent plomb spécifique est ≥ 30 pour au moins deux tensions de tube différant d'au moins 20 kV l'une de l'autre dans une plage de tensions comprise entre 60 et 125 kV conformément à IEC 1331-1/EN 61331, et en particulier ≥ 32 et en particulier ≥ 34, les tensions de tube différant en particulier de 40 kV, 45 kV et en particulier 65 kV l'une de l'autre.
  8. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que la couche de support est composée d'un matériau de plastisol PVC et/ou de polyuréthane et/ou de polyester.
  9. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que la proportion de la préparation polymère dans la couche absorbant les rayonnements est > 0 et ≤ 20 % en poids et la proportion de particules absorbant les rayonnements est ≥ 80 % en poids et < 100 % en poids, en particulier la proportion de la préparation polymère est comprise entre 10 et 20 % en poids et la proportion de particules absorbant les rayonnements est comprise entre 80 et 90 % en poids.
  10. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que les particules absorbant les rayonnements contiennent de l'étain, du bismuth, du baryum et/ou du tungstène ainsi que l'oxyde et les sels de ces métaux, ainsi que des mélanges de ces derniers.
  11. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que le stratifié multicouches présente une épaisseur comprise entre 0,3 et 1,2 mm, en particulier entre 0,3 et 0,5 mm, de préférence entre 0,35 et 0,45 mm.
  12. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en que la au moins une couche de support renferme des particules absorbant les rayonnements.
  13. Matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que la au moins une couche de support, sur son côté orienté à l'opposé de la couche absorbant les rayonnements, est lavable et/ou résistante à l'usure et/ou possède des propriétés textiles.
  14. Matériau absorbant les rayonnements selon l'une des revendications précédentes, caractérisé en ce que la couche de support est reliée intégralement à la couche absorbant les rayonnements.
  15. Procédé pour fabriquer un matériau de protection contre les rayonnements selon l'une des revendications précédentes, caractérisé en ce que l'on prépare, en particulier fabrique, une couche de support par raclage et séchage sur un substrat, en ce que l'on fabrique un matériau pour une couche absorbant les rayonnements à partir d'une préparation polymère liquide pouvant être coulée en y ajoutant des particules absorbant les rayonnements, en ce que l'on applique, verse ou étale ce matériau sur la couche de support, et en ce que l'on fait durcir le matériau de la couche absorbant les rayonnements par réticulation thermique et/ou chimique et/ou physique.
  16. Utilisation d'un matériau de protection contre les rayonnements selon l'une des revendications précédentes comme vêtement de protection contre les rayonnements, en particulier comme tablier de protection contre les rayonnements.
EP20030787749 2002-06-08 2003-06-10 Matiere de protection contre les rayonnements, procede de production d'une matiere de protection contre les rayonnements et utilisation de cette matiere Expired - Lifetime EP1512154B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE20208918U 2002-06-08
DE2002208918 DE20208918U1 (de) 2002-06-08 2002-06-08 Bleifreies Strahlenschutzmaterial
PCT/EP2003/006085 WO2004017333A1 (fr) 2002-06-08 2003-06-10 Matiere de protection contre les rayonnements, procede de production d'une matiere de protection contre les rayonnements et utilisation de cette matiere

Publications (2)

Publication Number Publication Date
EP1512154A1 EP1512154A1 (fr) 2005-03-09
EP1512154B1 true EP1512154B1 (fr) 2010-03-31

Family

ID=29285776

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20030787749 Expired - Lifetime EP1512154B1 (fr) 2002-06-08 2003-06-10 Matiere de protection contre les rayonnements, procede de production d'une matiere de protection contre les rayonnements et utilisation de cette matiere

Country Status (7)

Country Link
US (2) US20060151749A1 (fr)
EP (1) EP1512154B1 (fr)
JP (1) JP4620460B2 (fr)
AT (1) ATE463035T1 (fr)
AU (1) AU2003285657A1 (fr)
DE (2) DE20208918U1 (fr)
WO (1) WO2004017333A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4268162B2 (ja) * 2005-10-18 2009-05-27 日本特装株式会社 車両用放射線防護装置
US20110165373A1 (en) * 2010-01-07 2011-07-07 BIoXR, LLC Radio-opaque films of laminate construction
US20140151584A1 (en) * 2012-10-29 2014-06-05 Bloxr Corporation Nuclear radiation shields, shielding systems and associated methods
US9114121B2 (en) 2010-01-07 2015-08-25 Bloxr Solutions, Llc Radiation protection system
US8754389B2 (en) * 2010-01-07 2014-06-17 Bloxr Corporation Apparatuses and methods employing multiple layers for attenuating ionizing radiation
JP5791281B2 (ja) * 2010-02-18 2015-10-07 キヤノン株式会社 放射線検出装置及び放射線検出システム
WO2013040666A1 (fr) * 2011-09-23 2013-03-28 Planideia Confecção De Vestuário De Proteção Ltda. - Epp Matériaux élastomères radio-opaques à liaisons carbone-carbone, procédé de préparation et applications associés
CN102496396B (zh) * 2011-11-16 2013-11-06 哈尔滨工业大学 稀土/钨/聚乙烯复合梯度防核辐射材料及其制备方法
CN102648783A (zh) * 2012-05-19 2012-08-29 扬州锦江有色金属有限公司 一种设有防核辐射合金纤维丝织层的防护鞋
CN102664050B (zh) * 2012-05-28 2014-10-29 丁俊 一种辐射防护材料
USD751256S1 (en) 2013-08-22 2016-03-08 Gonaprons Llc Radiation shielding device
US9534089B2 (en) * 2014-07-11 2017-01-03 The Boeing Company Temperature-resistant silicone resins
US10128010B2 (en) 2014-12-15 2018-11-13 Tokuyama Corporation Radiation shielding material and production method therefor
CN108586777A (zh) * 2018-04-19 2018-09-28 孙海 一种无铅防射线辐射橡胶复合材料的制备方法
JP7092302B2 (ja) 2018-05-31 2022-06-28 早川ゴム株式会社 放射線遮蔽指サック
RU2709596C1 (ru) * 2019-02-15 2019-12-18 Акционерное общество "Научно-исследовательский институт резиновых покрытий и изделий" (АО "НИИРПИ") Терморадиационностойкая эластомерная композиция
CN113674888A (zh) * 2021-08-20 2021-11-19 山东双鹰医疗器械有限公司 一种X、γ射线防护硬质材料及制备方法
CN113696369A (zh) * 2021-09-08 2021-11-26 西安工程大学 一种基于热塑性弹性体的X、γ射线防护体的制备方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3200085A (en) * 1959-03-02 1965-08-10 Arthur L Barber Jr Radiation barrier material and method of making the same
US3061491A (en) * 1959-07-24 1962-10-30 Cordo Chemical Corp Laminated structures
US3627707A (en) * 1968-12-31 1971-12-14 Ball Corp Thixotropic polyvinyl chloride plastisol composition
US4056161A (en) * 1975-10-30 1977-11-01 Tillotson Corporation Sound attenuation material
JPS56131649A (en) * 1980-03-21 1981-10-15 Showa Denko Kk Neutron shield
US4938233A (en) * 1987-08-03 1990-07-03 Techton, Inc. Radiation shield
GB9300564D0 (en) 1993-01-12 1993-03-03 Smith & Nephew Protective articles
JP3557864B2 (ja) * 1996-09-24 2004-08-25 住友電気工業株式会社 放射線遮蔽材及びその製造方法
US6153666A (en) * 1998-07-16 2000-11-28 Bar-Ray Products, Inc. Radiation-attenuating sheet material
US6232383B1 (en) * 1998-11-06 2001-05-15 Nurescell, Inc. Nuclear resistance cell and methods for making same
US6828578B2 (en) * 1998-12-07 2004-12-07 Meridian Research And Development Lightweight radiation protective articles and methods for making them
DE20100267U1 (de) * 2001-01-08 2001-06-28 Thiess Axel Bleifreies Röntgenschutzmaterial
DE10234159C1 (de) * 2002-07-26 2003-11-06 Heinrich Eder Blei-Ersatzmaterial für Strahlenschutzzwecke
US7196023B2 (en) * 2003-04-10 2007-03-27 Kappler, Inc. Chemically resistant radiation attenuation barrier

Also Published As

Publication number Publication date
US20080128660A1 (en) 2008-06-05
EP1512154A1 (fr) 2005-03-09
WO2004017333A1 (fr) 2004-02-26
US7645506B2 (en) 2010-01-12
DE20208918U1 (de) 2003-10-23
ATE463035T1 (de) 2010-04-15
JP4620460B2 (ja) 2011-01-26
JP2005529352A (ja) 2005-09-29
US20060151749A1 (en) 2006-07-13
DE50312570D1 (de) 2010-05-12
AU2003285657A1 (en) 2004-03-03

Similar Documents

Publication Publication Date Title
EP1512154B1 (fr) Matiere de protection contre les rayonnements, procede de production d&#39;une matiere de protection contre les rayonnements et utilisation de cette matiere
DE19955192C2 (de) Verfahren zur Herstellung eines Strahlenschutzmaterials
DE112009002123B4 (de) Bleifreier Röntgenabschirmungs-Gummiverbundwerkstoff und Verfahren zu dessen Herstellung
DE1558645C3 (de) Flexibles Strahlenschutzmatenal und Verfahren zu seiner Herstellung
US6153666A (en) Radiation-attenuating sheet material
EP1576619B1 (fr) Melange sans plomb utilise en tant qu&#39;additif de protection contre les rayonnements
DE102004015613A1 (de) Strahlenschutzmaterial auf Silikonbasis
DE1650105B2 (de) Dichtungswerkstoff
EP3249006A1 (fr) Compositions d&#39;élastomère ou de caoutchouc et leur procédé de fabrication
DE10340124A1 (de) Bleifreie Mischung als Strahlenschutz-Additiv
DE2905977A1 (de) Vulkanisierbare gummimischung mit geringem schwefelausschlag
DE2155375B2 (de) Mischungen von fluorierten Elastomeren
DE3409414C2 (de) Polyamid-Gummi-Gemisch
WO2005023116A1 (fr) Materiau leger de protection contre les rayonnements destine a une grande gamme d&#39;energies
DE3323151C2 (fr)
EP1549220B1 (fr) Materiau de protection contre les rayonnements a base de silicone
DE2550664B2 (de) Verfahren zum Herstellen eines druckmittelführenden Schlauches
DE2530039B2 (de) Verfahren zum Verbinden von Butadien-Acrylnitril-Kautschuk mit Metallen
KR102334663B1 (ko) 무납 감마선 차폐 시트 및 이의 제조방법
DE1939926B2 (de) Thermoplastische Massen und Verfahren zu deren Herstellung
DE2252686A1 (de) Polyvinylchloridpraeparate
EP0111287A2 (fr) Masses moulables, conductrices de l&#39;électricité, non réticulables, à base de matières synthétiques thermoplastiques et de noir de fumée
DE2954186C2 (de) Anordnung zur Modifizierung der Festigkeit eines Kunststoffteiles durch Bestrahlung
EP0769539B1 (fr) Composition pour revêtement à base d&#39;une dispersion de polyoléfine non aqueux et procédé pour sa préparation
WO2005049713A1 (fr) Materiau de protection contre les rayonnements destine a des vetements de protection tels que des tabliers et similaires

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

17P Request for examination filed

Effective date: 20041117

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 20050411

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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): 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

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: MICHELI & CIE SA

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 50312570

Country of ref document: DE

Date of ref document: 20100512

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100712

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

BERE Be: lapsed

Owner name: PAUL HARTMANN A.G.

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100802

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

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: 20110104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100610

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100610

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100331

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20160628

Year of fee payment: 14

Ref country code: DE

Payment date: 20160622

Year of fee payment: 14

Ref country code: CH

Payment date: 20160621

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20160621

Year of fee payment: 14

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50312570

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170610

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180103

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170610

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630