EP0953555B1 - Procédé de préparation de particules de propergols et explosifs fusibles - Google Patents

Procédé de préparation de particules de propergols et explosifs fusibles Download PDF

Info

Publication number
EP0953555B1
EP0953555B1 EP19990105812 EP99105812A EP0953555B1 EP 0953555 B1 EP0953555 B1 EP 0953555B1 EP 19990105812 EP19990105812 EP 19990105812 EP 99105812 A EP99105812 A EP 99105812A EP 0953555 B1 EP0953555 B1 EP 0953555B1
Authority
EP
European Patent Office
Prior art keywords
emulsion
matrix liquid
melt
particles
adn
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
EP19990105812
Other languages
German (de)
English (en)
Other versions
EP0953555A1 (fr
Inventor
Ulrich Dipl.-Ing. Teipel
Horst Dr. Krause
Karlfred Leisinger
Thomas Heintz
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.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of EP0953555A1 publication Critical patent/EP0953555A1/fr
Application granted granted Critical
Publication of EP0953555B1 publication Critical patent/EP0953555B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0066—Shaping the mixture by granulation, e.g. flaking
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/005—By a process involving melting at least part of the ingredients
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt

Definitions

  • the invention relates to a process for the preparation of substantially spherical particles of meltable, moisture-sensitive propellants and explosives, and oxidizers, in particular ammonium dinitramide (ADN), by melting the explosive substance melt in a matrix liquid in which the explosive is not soluble or only sparingly soluble, emulsified, the emulsion is cooled below the melting point of the explosive material with recrystallization of the dispersed droplets to solid particles and the solid particles are separated from the matrix liquid.
  • ADN ammonium dinitramide
  • Ammonium dinitramide is of great importance as an oxidizer for fuels and as an explosive.
  • compactable particles are desired for both manufacturing and processing.
  • conventional crystalline propellants and explosives usually very irregular particles. This is especially true for ADN.
  • the grain properties especially the grain shape, let often improve by recrystallization of the crystalline substances from a solution.
  • the crystalline substance is usually dissolved by heating in one or more suitable solvents and crystallized by defined cooling, the substance. If necessary, this process can be carried out several times. As a result of the differences in solubility between substance and impurities unwanted impurities are separated because they remain either unresolved from the outset, or because they also go into solution, because of their low concentration remain in the matrix liquid when the crystals have already precipitated.
  • GB 2 187 726 A describes a process for producing a solid explosive mixture, so-called emulsion explosives, in which a discontinuous phase in the form of an oxidizing salt is heated and melted and contained in a continuous phase serving as fuel, e.g. Paraffin oil or wax, emulsified.
  • fuel e.g. Paraffin oil or wax
  • additives such as emulsifiers or crystallization nuclei are added to the emulsion in order to obtain a finely dispersed discontinuous phase and to prevent confluence of the dispersed droplets.
  • the emulsion is cooled to obtain an explosive mixture in which the oxidizing salts are finely dispersed so as to prevent spontaneous detonation such as may occur with coarsely dispersed particles.
  • From US 3,522,334 is a process for the preparation of spherical particles of a mixture of nitronium perchlorate and lithium perchlorate having a melting point of less than 120 ° C, wherein the mixture is melted and in an inert, with LiClO 4 and NO 2 ClO 4 immiscible liquid, in particular halogenated hydrocarbons, is dispersed. After cooling and solidification of the particles, they are separated from the liquid.
  • WO 97/47571 describes a corresponding process for producing spherical particles from explosives, in particular ADN.
  • DE 1 467 203 discloses a process for the preparation of spherical, non-caking ammonium nitrate (AN), wherein the AN is melted at about 170 ° C to 180 ° C and dispersed in an inert suspending agent. After cooling the suspension to about 130 ° C, the suspending agent is separated from the spherical AN by means of a continuous centrifuge and recirculated. In order to counteract clumping of the finished product, unspecified anti-caking agents are added to the suspension, which adsorptively adhere to the AN.
  • AN spherical, non-caking ammonium nitrate
  • the invention has the object of providing a method of the type mentioned for the production of uniform, in particular spherical particles meltable, moisture-sensitive propellants and explosives or oxidizers, in particular ammonium dinitramide (ADN), to the effect that particles are obtained with a defined particle size whose diameter in can be varied over a wide range from a few ⁇ m to a few mm.
  • ADN ammonium dinitramide
  • this object is achieved in a method of the type mentioned in that for emulsifying and to reduce coalescence silicon dioxide for changing the surface tension between melt and matrix liquid is added.
  • the propellant or explosive or the oxidizer is converted in a manner known per se into a melt and combined with a matrix liquid in which the material to be recrystallized is not or only slightly soluble.
  • the matrix liquid ensures that the moisture-sensitive propellants and explosives as well as oxidants, in particular the highly hygroscopic ADN, during the recrystallization no water, e.g. Humidity, absorb. It is selected so that the molten substance can be emulsified.
  • the subsequent separation of the phase mixture is based solely on the different melting points of starting material and matrix liquid and not due to changes in concentration of a solution.
  • the interfacial tension between the two components and the viscosity of the outer phase can be changed, thus affecting the production conditions and the stability of the emulsion.
  • emulsifiers and stabilizers By adding various additives such as emulsifiers and stabilizers, the interfacial tension between the two components and the viscosity of the outer phase can be changed, thus affecting the production conditions and the stability of the emulsion.
  • a likewise hydrophobic emulsifier in the form of silica increases the stability of the emulsion and reduces the coalescence, in which the emulsified droplets converge to form a kontiunierlichen phase. Consequently, an emulsion of finer droplets can be achieved by adding such an emulsifier under otherwise identical conditions.
  • a stabilizer under otherwise identical conditions however, larger droplets of the emulsified substance are obtained.
  • spherical particles having defined particle properties such as average particle size, particle size distribution, specific surface, are obtained with the method according to the invention.
  • the spherical particles not only lead to an optimum bulk and tap density, but also to a high energy density and a favorable burning behavior.
  • the emulsion consisting of ADN droplets as a disperse phase and a matrix liquid and tempered above the melting point of ADN is subsequently cooled below the melting point of ADN, so that the dispersed ADN droplets crystallize out to solid particles.
  • the concentration of molten material in the matrix liquid is preferably less than 50% by mass and in particular less than 60% by mass.
  • the matrix liquid which is separated after crystallization can be reused and, for example, circulated.
  • the melt can be mixed with additives which are soluble in the propellant or explosive or in the oxidizer, with which the subsequent product quality of the ADN particles with regard to stability, sensitivity or flowability can be improved.
  • additives which are soluble in the propellant or explosive or in the oxidizer, with which the subsequent product quality of the ADN particles with regard to stability, sensitivity or flowability can be improved.
  • the matrix liquid are mainly oils, e.g. Paraffin oil or silicone oil, in question, which have a hydrophobic character.
  • the emulsion is prepared by introducing energy into the fluid system. This can be done by shaking, stirring, by introducing vibrations into the system, for example by means of ultrasound, or else by injecting the melt into the matrix liquid or vice versa.
  • the crystallization process can, in addition to the application of a temperature gradient specifically required for the crystallization, be controlled both by the introduction of mechanical energy and by the addition of nuclei.
  • the input of mechanical energy in the crystallization to produce a very finely crystalline product can be carried out by means of stirrer or ultrasound, which can be controlled by the concentration of the disperse phase.
  • the process according to the invention can be carried out both continuously and batchwise.
  • a discontinuous process variant in which the preparation of the emulsion and the crystallization of the dispersed droplets can be carried out in a reactor, for example, various stirrers, such as blade or propeller, or discontinuous Zahnzranzdispergierer are suitable for preparing the emulsion.
  • stirring energy Under the influence of stirring energy, the emulsion is subsequently cooled so that spherical particles crystallize out.
  • the two process steps of emulsification and recrystallization can also be carried out separately in time and place, wherein the emulsion is conveyed after its preparation in a second reactor in which the recrystallization, for example by a suitable temperature gradient, can be influenced.
  • the emulsion is first prepared by colloid mills, static mixers, or continuous sprocket dispersing machines, and then into the crystallization zone, e.g. in a tubular reactor or cascade crystallizer.
  • a separation unit for separating the recrystallized particles from the matrix liquid, the separation being able to take place by sedimentation, filtration or centrifuging. After separation of the particles, they are washed with a suitable solvent and dried.
  • spherical ADN Preparation of spherical ADN from an emulsion with a concentration of 12% by mass.
  • Paraffin oil is used as the matrix liquid of the emulsion.
  • silicon dioxide (hydrophobic) is added.
  • spherical ADN particles crystallize out. The average grain diameter produced is 420 ⁇ m.
  • the spherical ADN is then rinsed with n-heptane and dried.
  • FIG. 1 shows crystalline ammonium dinitramide (ADN) from the synthesis.
  • the grain is rugged and edgy. Grain size and grain shape vary greatly.
  • FIGS. 2 and 3 show spherical particles of ammonium dinitramide (ADN) having a mean grain diameter below 500 .mu.m, produced from a paraffin oil emulsion by the process according to the invention, in two different magnification scales.
  • the grain is almost exactly spherical; the grain spectrum is relatively narrow.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Medicinal Preparation (AREA)

Claims (11)

  1. Procédé de production de particules essentiellement sphériques de matériaux carburants et explosifs, fusibles, sensibles à l'humidité, ainsi que d'oxydants, en particulier de dinitramide d'ammonium (ADN), selon lequel on fait fondre le matériau explosif, on émulsionne la masse fondue dans une matrice liquide dans laquelle le matériau explosif n'est pas ou n'est que difficilement soluble, on refroidit l'émulsion en dessous du point de fusion du matériau explosif avec recristallisation des gouttes dispersées en particules solides, et on sépare les particules solides de la matrice liquide,
    caractérisé en ce que
    pour émulsionner et pour diminuer la coalescence on ajoute du dioxyde de silicium pour modifier la tension superficielle entre la masse fondue et la matrice liquide.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    la concentration de la masse fondue dans la matrice liquide est inférieure à 50 % en masse.
  3. Procédé selon la revendication 2,
    caractérisé en ce que
    la concentration de la masse fondue dans la matrice liquide est inférieure à 40 % en masse.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce que
    comme matrice liquide on utilise des huiles, en particulier une huile de paraffine et/ ou une huile de silicone.
  5. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    on ajoute à la masse fondue des additifs qui y sont solubles afin d'améliorer les propriétés des particules recristallisées.
  6. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    on produit l'émulsion à partir de la masse fondue et de la matrice liquide par apport d'énergie mécanique.
  7. Procédé selon la revendication 6,
    caractérisé en ce que
    comme énergie mécanique on apporte une énergie sonore, en particulier des ultrasons.
  8. Procédé selon l'une des revendications 1 à 7,
    caractérisé en ce qu'
    on produit l'émulsion par pulvérisation de la masse fondue dans la matrice liquide.
  9. Procédé selon l'une des revendications 1 à 8,
    caractérisé en ce que
    lors du refroidissement de l'émulsion on ajoute des germes de cristallisation.
  10. Procédé selon l'une des revendications 1 à 9,
    caractérisé en ce que
    lors du refroidissement de l'émulsion on influe sur la cristallisation par apport d'énergie mécanique.
  11. Procédé selon la revendication 10,
    caractérisé en ce que
    lors de son refroidissement, on soumet l'émulsion, à une énergie sonore, en particulier à des ultrasons.
EP19990105812 1998-04-16 1999-03-23 Procédé de préparation de particules de propergols et explosifs fusibles Expired - Lifetime EP0953555B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19816853 1998-04-16
DE1998116853 DE19816853A1 (de) 1998-04-16 1998-04-16 Verfahren zur Herstellung von Partikeln schmelzfähiger Treib- und Explosivstoffe

Publications (2)

Publication Number Publication Date
EP0953555A1 EP0953555A1 (fr) 1999-11-03
EP0953555B1 true EP0953555B1 (fr) 2005-09-21

Family

ID=7864703

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19990105812 Expired - Lifetime EP0953555B1 (fr) 1998-04-16 1999-03-23 Procédé de préparation de particules de propergols et explosifs fusibles

Country Status (3)

Country Link
EP (1) EP0953555B1 (fr)
DE (2) DE19816853A1 (fr)
NO (1) NO312954B1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10201937B4 (de) * 2002-01-19 2005-08-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von mit Additiven versetztem Ammoniumdinitramid (ADN)
FR2884244B1 (fr) * 2005-04-12 2007-07-06 Snpe Materiaux Energetiques Sa Obtention de cristaux de dinitroamidure d'ammonium (adn); cristaux d'adn et les composites energetiques en contenant.
FR3081864B1 (fr) * 2018-05-30 2022-03-18 Arianegroup Sas Obtention de cristaux de dinitroamidure d'ammmonium (adn) ; cristaux d'adn et les composites energetiques en contenant
DE102020122328B3 (de) 2020-08-26 2021-08-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verfahren zur Herstellung von Partikeln aus Ammoniumdinitramid (ADN)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL85445C (fr) * 1955-02-23
US3522334A (en) * 1961-05-09 1970-07-28 Exxon Research Engineering Co Preparation of spherical solid oxidizer pellets from nitronium perchlorate-lithium perchlorate mixture
DE1467203B2 (de) * 1964-09-09 1974-03-28 Bundesrepublik Deutschland Vertr. Durch Den Bundesminister Der Verteidigung, 5300 Bonn Verfahren zum Herstellen von kugeligem Ammoniumnitrat
US3468986A (en) * 1966-11-15 1969-09-23 David J Watanabe Method for producing a solid particulate material
US4118797A (en) * 1977-10-25 1978-10-03 Energy And Minerals Research Co. Ultrasonic emulsifier and method
IT1096661B (it) * 1978-06-13 1985-08-26 Montedison Spa Procedimento per la preparazione di prodotti in forma sferoidale solidi a temperatura ambiente
EP0238210A3 (en) * 1986-03-14 1989-05-24 Imperial Chemical Industries Plc Solid explosive composition
BE1002001A4 (fr) * 1988-02-18 1990-05-15 Mitsubishi Mining & Cement Co Procede de preparation de microspheres ceramiques.
JPH07503798A (ja) * 1992-02-14 1995-04-20 リサーチ　ラボラトリース　オブ　オーストラリア　プロプライエタリー　リミテッド 静電写真法に有用な球形粒子
US5688742A (en) * 1995-08-18 1997-11-18 Rohm And Haas Company Water based formation of a beaded product
US5801453A (en) * 1996-06-11 1998-09-01 United Technologies Corporation Process for preparing spherical energetic compounds

Also Published As

Publication number Publication date
DE59912567D1 (de) 2006-02-02
DE19816853A1 (de) 1999-10-21
NO991178D0 (no) 1999-03-10
NO991178L (no) 1999-10-18
EP0953555A1 (fr) 1999-11-03
NO312954B1 (no) 2002-07-22

Similar Documents

Publication Publication Date Title
EP0399266B1 (fr) Préparaton de dispersiones sphérique par cristallisation d'émulsiones
EP1044712B1 (fr) Agent antimousse pour milieux aqueux
DE3510761A1 (de) Kristallisationsverfahren
DE2948332A1 (de) Wasser-in-oel-sprengmittelemulsion
EP1281420B1 (fr) Processus de crystallisation faisant appel aux ultrasons
DE2923311C2 (de) Verfahren und Vorrichtung zur Herstellung von rotationssymmetrischen Sprengkörpern für Hohlladungen
EP0953555B1 (fr) Procédé de préparation de particules de propergols et explosifs fusibles
DE2054870C3 (de) Verfahren zum Entparaffinieren von paraffinhaltigen Erdölfraktionen
EP1256558A2 (fr) Procédé de production de cristaux à partir de propergols, explosifs et agents oxydants en solution dans un solvant
EP0046247B1 (fr) Procédé pour la fabrication de dispersions et matériaux photographiques
DE102004004964B4 (de) Verfahren zur Herstellung von Komposit-Partikeln aus kristallinen Explosivstoffen und deren Verwendung
EP1308193B1 (fr) Procédé pour la production de cristaux à partir de solutions contenant des solides dissous
EP1331213A2 (fr) Procédé de fabrication de dinitramide d'ammonium contenant des additifs
DE102006025187B4 (de) Verfahren zur Herstellung von wenig stoßempfindlichen Sprengstoffpartikeln
DE69224230T2 (de) Geschäumten Sensibilisator enthaltender Sprengstoff
DE102004002318A1 (de) Verfahren zur Herstellung feindisperser kristallinger Treib-, Explosivstoffe und Oxidatoren
DE1467203C3 (fr)
EP1090894A1 (fr) Procédé de fabrication de fines particules d'explosifs
DE2308154C3 (de) Gießbare Sprengstoffmischungen auf der Basis von Hexogen, Oktogen und Trinitroluol sowie ihre Herstellungs- und Verarbeitungsverfahren
CA2183009A1 (fr) Methode de desemulsification
EP0056491B1 (fr) Procédé de préparation de triaminotrinitrobenzène à gros grains
DE309618C (fr)
DE2214698C3 (de) Verfahren zur Herstellung von Mikrokapseln
EP1055652A1 (fr) Procédé de fabrication de fines particules d'explosifs
EP1297756A1 (fr) Compositions de stérols sphériques, leurs préparation et utilisation

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: A1

Designated state(s): CH DE ES FR GB LI NL SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWAN

17P Request for examination filed

Effective date: 20000422

AKX Designation fees paid

Free format text: CH DE ES FR GB LI NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DERANGEWAND

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DERANGEWAND

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RBV Designated contracting states (corrected)

Designated state(s): CH DE ES FR GB LI NL SE

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): CH DE ES FR GB LI NL SE

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: 20050921

Ref country code: GB

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: 20050921

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59912567

Country of ref document: DE

Date of ref document: 20051027

Kind code of ref document: P

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

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: 20051221

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

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: 20060101

REF Corresponds to:

Ref document number: 59912567

Country of ref document: DE

Date of ref document: 20060202

Kind code of ref document: P

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

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

Effective date: 20060331

Ref country code: CH

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

Effective date: 20060331

GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 20050921

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: 20060622

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061020

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EN Fr: translation not filed
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050921

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

Ref country code: DE

Payment date: 20180322

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59912567

Country of ref document: DE