EP1333015B1 - Procédé semi-continu d'obtention d'un chargement explosif composite à matrice polyuréthanne, ledit procédé mettant en oeuvre deux composants - Google Patents

Procédé semi-continu d'obtention d'un chargement explosif composite à matrice polyuréthanne, ledit procédé mettant en oeuvre deux composants Download PDF

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Publication number
EP1333015B1
EP1333015B1 EP03290123A EP03290123A EP1333015B1 EP 1333015 B1 EP1333015 B1 EP 1333015B1 EP 03290123 A EP03290123 A EP 03290123A EP 03290123 A EP03290123 A EP 03290123A EP 1333015 B1 EP1333015 B1 EP 1333015B1
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EP
European Patent Office
Prior art keywords
component
process according
explosive
components
pasty
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
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EP03290123A
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German (de)
English (en)
French (fr)
Other versions
EP1333015A3 (fr
EP1333015A2 (fr
Inventor
Jean-Paul Augier
Bernard Mahe
Alain Bonnel
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Eurenco SA
Original Assignee
Eurenco SA
Eurenco France SA
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Priority to SI200331729T priority Critical patent/SI1333015T1/sl
Publication of EP1333015A2 publication Critical patent/EP1333015A2/fr
Publication of EP1333015A3 publication Critical patent/EP1333015A3/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033Shaping the mixture
    • C06B21/0058Shaping the mixture by casting a curable composition, e.g. of the plastisol type
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • the present invention is in the military field, more particularly in the field of explosive ordnance, such as bombs and shells.
  • composite explosive conventionally means a functionally detachable pyrotechnic composition consisting of a solid polymeric matrix, generally polyurethane, filled, said charge being pulverulent and containing an organic nitro-explosive charge, for example hexogen, octogen, ONTA (oxynitrotriazole), or a mixture of at least two of these compounds.
  • Composite explosive shipments and the manner of obtaining them are for example described by J. QUINCHON, powders, propellants and explosives, volume 1, explosives, Technique and Documentation, 1982, pages 190-192 .
  • the pulverulent filler is mixed in a kneader with a liquid polymerizable resin, for example a hydroxyl-terminated prepolymer.
  • a paste is obtained that can be poured into a mold and then polymerized by cooking.
  • resin crosslinking agents, catalysts and other additives moldings of various characteristics can be obtained.
  • the dough When mixing is complete, the dough should be used within a short time (pot life).
  • pot life The lengthening of the pot life by a reduction in the rate of crosslinking catalyst has as counterpart an increased polymerization time, the temperature being limited, inter alia, by the pyrotechnic nature of certain constituents.
  • this "batch" process proves to be well-adapted for making large objects such as submarine mines, torpedoes and bombs, it proves to be very penalizing and expensive to manufacture a large quantity of small objects molded at a high rate, for example to make several hundred shells diameter of about 50 to 100mm each containing a few hundred grams to a few kilograms of composite explosive from a kneaded 1 to 3 t of dough.
  • JM TAUZIA in a communication entitled “Some comments on Processing Energetic Materials” at Symposium “Compatibility and Processing” organized by the American Defense Prepardness Association (ADPA) on 23-25 October 1989 in Virginia Beach (USA) is) suggests, to solve this problem, a two-component process in which 2 chemically stable polymeric components and having approximately the same filler content and viscosity are first made from the constituents, discontinuously in kneaders.
  • a first disadvantage is that it is very difficult to continuously mix the 2 pasty components to obtain a homogeneous product.
  • a second disadvantage is that the 2 components are pyrotechnically active (presence of explosive charges) and must therefore both be made and stored in secure facilities.
  • a third drawback is that the solid polymeric matrix of the composite explosive finally obtained is different from that which is obtained with the same constituents in the same proportions, according to the conventional "batch” method.
  • the isocyanate component is polymeric.
  • the fact of preparing, in an intermediate manner, an isocyanate prepolymer from the starting isocyanate monomer results in obtaining a solid polyurethane matrix different from that obtained according to the "batch” process by directly mixing all the isocyanate monomer and any the hydroxyl prepolymer.
  • the main subject of the present invention is an improvement of this two-component process and proposes a two-component semi-continuous process for obtaining a composite explosive charge with a polyurethane matrix, presenting neither the disadvantages of the conventional "batch" method nor the aforementioned drawbacks. of the two-component semi-continuous process described by JM TAUZIA.
  • a composite explosive charge with a polyurethane matrix can be obtained by a simple and inexpensive two-component semi-continuous process, which does not require requalification of the final product, thanks to a very precise combination of technical characteristics relating to the distribution of constituents in the 2 components and to the mass ratio of mixing of the 2 components.
  • the subject of the present invention is a semi-continuous process for obtaining composite explosive charges consisting of a filled polyurethane solid matrix whose charge is solid, pulverulent and comprises at least one organic nitrated explosive, by introduction into molds. of a pasty explosive composition and thermal crosslinking of this composition, said composition being obtained by mixing constituents essentially comprising a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a solid filler pulverulent composition comprising at least one organic nitro explosive.
  • the components A and B do not have the same viscosity, that one is pasty and comprises all of the polyol prepolymer and that the other is liquid and comprises all of the polyisocyanate monomer, such as, without modification chemical, especially without prepolymerization using a polyol.
  • component A Only component A is pyrotechnically active, which considerably limits the safety constraints, and the mixing of components A and B is easily homogenized.
  • the physicochemical, mechanical, detonation and vulnerability properties of the final product are identical to those of the product obtained according to the conventional "batch" process from the same constituents in the same proportions, which avoids a penalizing requalification of the product. .
  • components A and B are completely independent of the casting operations and can be performed during masked times. These components A and B can be stored if necessary for several weeks before being mixed.
  • the process according to the invention is moreover totally independent of the pot life because small amounts of components A and B are rapidly and continuously mixed, which makes it possible to increase the percentage of crosslinking catalyst and to reduce accordingly the crosslinking time of the pasty explosive composition in the mold and / or to achieve this crosslinking at a lower temperature.
  • the pasty explosive composition is obtained from the usual constituents used according to the prior methods and which are well known to those skilled in the art.
  • These constituents essentially comprise a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a pulverulent filler comprising at least one organic nitrated explosive.
  • the sum of the contents by weight of polyol prepolymer, plasticizer, polyisocyanate monomer and pulverulent filler represents between 98% and 100% of all the constituents.
  • the physical states, solid, liquid, pasty, constituents and compositions should be understood, in the present description, as the physical states at room temperature (about 20 ° C) and at atmospheric pressure (about 0.1 MPa).
  • organic nitro explosive is conventionally understood to mean an explosive selected from the group consisting of aromatic nitro explosives (comprising at least one C-NO 2 group , the carbon atom being part of an aromatic ring) , nitric ester explosives (comprising at least one CO-NO 2 group ) and nitramine explosives (comprising at least one CN-NO 2 group ).
  • the organic nitrated explosive is selected from the group consisting of hexogen, octogen, pentrite, 5-oxo-3-nitro-1,2,4-triazole (ONTA), triaminotrinitrobenzene, nitroguanidine and mixtures thereof, i.e., all mixtures of at least two of the above compounds.
  • the organic nitrated explosive is selected from the group consisting of hexogen, octogen, ONTA and mixtures thereof.
  • the content of organic nitro explosive is between 15% and 90% by weight relative to the composite explosive and the content of solid powdery charge is between 75% and 90% by weight relative to the explosive. composite.
  • the pulverulent solid filler consists only of organic nitro explosive.
  • the pulverulent solid filler also comprises at least one other compound than the organic nitro explosive.
  • reducing metal preferably selected from the group consisting of aluminum, zirconium, magnesium, tungsten, boron and mixtures thereof.
  • the reducing metal is aluminum.
  • the reducing metal content may for example be between 0% and 35% by weight relative to the composite explosive.
  • the pulverulent filler may also comprise, in combination or not with a reducing metal, a mineral oxidant, preferably chosen from the group consisting of ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  • a mineral oxidant preferably chosen from the group consisting of ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  • the mineral oxidant content may for example be between 0% and 45% by weight relative to the composite explosive.
  • the pulverulent solid filler comprises at least one other compound than the organic nitro explosive
  • this other compound is preferably selected from the group consisting of ammonium perchlorate, aluminum and mixtures thereof.
  • the polyol prepolymer is a more or less viscous liquid.
  • Its number-average molecular weight (Mn) is preferably between 500 and 10,000 and is preferably selected from the group consisting of polyisobutylene polyols, polybutadiene polyols, polyether polyols, polyester polyols and polysiloxane polyols. Hydroxyl-terminated polybutadiene is particularly preferably used.
  • the polyisocyanate monomer is a liquid preferably selected from the group consisting of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethylene diisocyanate (MDCI), hexamethylene diisocyanate (HMDI), biuret trihexane isocyanate (BTHI ), 3,5,5-trimethyl-1,6-hexamethylene diisocyanate, and mixtures thereof.
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • MDCI dicyclohexylmethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • BTHI biuret trihexane isocyanate
  • IPDI Intra-PDI or MDCI is used.
  • the plasticizer is also a liquid, preferably a monoester such as isodecyl pelargonate (IDP) or a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
  • a monoester such as isodecyl pelargonate (IDP)
  • a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
  • a monoester such as isodecyl pelargonate (IDP) or a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
  • DOP dioctyl phthalate
  • DOZ dioctyl azelate
  • DOA dioctyl adipate
  • all the constituents may also comprise at least one additive selected from the group consisting of crosslinking catalysts (NCO / OH reaction catalysts), wetting agents, antioxidants and agents. binder-load adhesion.
  • additives selected from the group consisting of crosslinking catalysts (NCO / OH reaction catalysts), wetting agents, antioxidants and agents. binder-load adhesion.
  • tin dibutyldilaurate As a crosslinking catalyst, tin dibutyldilaurate (DBTL) is preferably used, but it is also possible to use any other catalyst well known to those skilled in the art, especially other organic compounds of tin such as a salt.
  • stannous carboxylic acid, a trialkyltin oxide, a dialkyltin dihalide or a dialkyltin oxide examples that may be mentioned are dibutyltin diacetate, diethyltin diacetate, dioctyltin dioxide and stannous octoate.
  • a catalyst a tertiary amine, especially a trialkylamine, or else an organic compound of bismuth, such as triphenylbismuth.
  • a lecithin such as soy lecithin or a siloxane is preferably used.
  • ditertiobutyl paracresol Ionol
  • MBP5 2,2'-methylenebis-4-methyl-6-tert-butylphenol
  • Binder-filler adhesion agent is preferably used triethylene pentamine acrylonitrile (TEPAN), or certain compounds derived from silanols such as triethoxysilyl-3-propyl succinic anhydride (C 13 H 24 O 6 Si).
  • TEPAN triethylene pentamine acrylonitrile
  • silanols such as triethoxysilyl-3-propyl succinic anhydride (C 13 H 24 O 6 Si).
  • the components may also include a polyurethane polymeric chain extender compound.
  • This compound is generally a low molecular weight polyol monomer of less than about 300, preferably a triol such as trimethylolpropane (TMP) or a diol such as dipropylene glycol.
  • TMP trimethylolpropane
  • diol such as dipropylene glycol.
  • component A comprises all of the plasticizer.
  • component B consists solely of the polyisocyanate monomer.
  • component A When the constituents comprise a chain extender compound, it is imperatively completely included in component A.
  • this additive may be distributed equally between the two components A and B, but, preferably, it is wholly included in component A.
  • the other constituents that the polyol prepolymer, the plasticizer, the polyisocyanate monomer and the pulverulent solid filler are exclusively selected from the group consisting of chain extender compounds, crosslinking catalysts, wetting agents, antioxidants and the binder-filler adhesion agents, the chain extender compounds being completely included in the component A, the crosslinking catalysts, the wetting agents, the antioxidants and the binder-filler adhesion agents being able to be indifferently distributed therein between the 2 components A and B.
  • they are preferably included in component A.
  • the components A and B are independently made by simple mixing, for example in a kneader, and are chemically stable, ie there is no chemical reaction between the mixed components of each component, and that all the constituents retain their structural identity, both during mixing and subsequent and independent storage of components A and B.
  • component A and component B are then continuously mixed in such a way that the component A / component B mass ratio is constant and between 95/5 and 99, 5 / 0.5, preferably between 98/2 and 99.2 / 0.8, for example close to 99.
  • This continuous mixing between the component A and the component B is carried out in a static mixer, a mixer well known to those skilled in the art, in the form of a pipe containing braces forcing the product which passes there to separate and then remix.
  • the components A and B are each contained in a pot equipped with a piston whose setting in motion, using a motor, allows the supply of components A and B of a convergent located upstream of the static mixer, so that the contents of the convergent flows into the static mixer.
  • the pressure on the mixture of components A and B in the convergent is preferably between 1 MPa and 10 MPa and the two pistons are preferably driven by the same engine.
  • the static mixer according to the invention is preferably composed of a plurality of duct-mounted series elements having a diameter of preferably between 15 mm and 60 mm.
  • mixing elements such as those sold commercially and well known to those skilled in the art, are used.
  • the pasty explosive composition is obtained with a flow rate of between 0.1 l / min and 51 / min, better still between 0.3 l / min and 11 l / min, for example close to 0.5 l / min. min.
  • components A and B are each contained in a pot equipped with a piston allows very precise dosages and a very regular supply, but it is also possible, for example, to supply the static mixer with the aid of metering pumps connected to storage bins of components A and B.
  • the static mixer is usually provided with a double jacket to allow adjustment of the temperature.
  • Each element can be regulated at a different temperature.
  • the last element can for example be regulated at the chosen temperature for the subsequent crosslinking of the explosive paste in the molds, the other elements upstream being regulated at a lower temperature.
  • Pots or bins containing components A and B may also be provided with a heating system.
  • component A and component B are mixed at a temperature of between 40 ° C. and 80 ° C.
  • the pasty explosive composition obtained after mixing the components A and B is introduced into a mold in which it then undergoes thermal crosslinking, in an oven for example.
  • This crosslinking results from the formation of urethane bridges due to the reaction of the hydroxyl functions of the polyol prepolymer and optionally of the chain extender compound with the isocyanate functional groups of the polyisocyanate monomer.
  • the crosslinking rate increases with temperature and catalyst content.
  • the mold is constituted by the envelope, generally metallic, of a munition, for example a shell.
  • the pasty explosive composition from the mixer is introduced automatically in a large series of molds, for example several hundred shells envelopes.
  • the crosslinking temperature of the pasty explosive composition introduced into the molds is between 15 ° C. and 80 ° C.
  • the crosslinking temperature is identical to or close to that at which component A and component B are mixed.
  • Example 1 Obtaining a composite explosive charge with a polyurethane matrix filled with hexogen A pasty component
  • Component B consists solely of isophorone diisocyanate (IPDI), ie polyisocyanate monomer.
  • the continuous mixing between the component A and the component B is carried out in a static mixer consisting of 13 elements connected in series of length 32 mm and diameter 32 mm, after transfer of each of the components A and B in a pot equipped with a piston.
  • the pot containing component A has a diameter of 300 mm and a height of 250 mm.
  • the pot containing component B has a diameter of 40 mm and a height of 250 mm.
  • the setting in motion of the 2 pistons allows the supply of components A and B of a convergent located upstream of the static mixer, so that on the one hand the component mass ratio A / component B is constant and equal to 99.14 / 0.86, and on the other hand that the content of the convergent flows into the static mixer.
  • the pressure on the mixture of components A and B in the convergent is 2.5 MPa.
  • the entire installation that is to say in particular the 2 pots containing the components A and B, the convergent and the 13 elements of the static mixer, is thermostated at 60 ° C.
  • the pasty explosive composition is obtained with a flow rate of 0.35 l / min.
  • the pasty explosive composition leaving the static mixer is cast, at room temperature, approximately 20 ° C., into metal molds of square section 80 mm ⁇ 80 mm and height 120 mm, previously arranged in a pour box connected to a valve located at the outlet of the static mixer, the box-valve seal being provided by a rubber.
  • the dynamic viscosity of the pasty explosive composition at the outlet of the static mixer is 5800 poises.
  • This mold loading operation is carried out under a partial vacuum of about 15 mmHg in the casing.
  • the molds After loading, the molds are introduced into an oven at 60 ° C. for 7 days, which makes it possible to crosslink the binder of the explosive composition and finally to obtain a composite explosive feed consisting of 12% by weight of polyurethane matrix and of 88% by weight of hexogen, whose density is 1.62 g / cm 3 .
  • the sensitivity to impact is 25 Joules.
  • the dynamic viscosity of the dough is then 4800 poises.
  • the pasty explosive composition obtained has the same weight composition as that obtained for Example 1.
  • This composition is then poured into molds identical to those used for Example 1, and then cured at 60 ° C. in an oven.
  • the composite explosive obtained after crosslinking at 60 ° C. has a density of 1.62 g / cm 3 , the same value as that of the composite explosive obtained in Example 1.
  • the sensitivity to friction and the impact sensitivity of the resulting composite explosive were also determined using the same methods as those used for Example 1.
  • the sensitivity to impact is 21 Joules.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
EP03290123A 2002-02-01 2003-01-17 Procédé semi-continu d'obtention d'un chargement explosif composite à matrice polyuréthanne, ledit procédé mettant en oeuvre deux composants Expired - Lifetime EP1333015B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200331729T SI1333015T1 (sl) 2002-02-01 2003-01-17 Polkontinuirni postopek za pripravo eksplozivnega kompozitnega naboja s poliuretanskim matriksom z uporabo dveh komponent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0201213 2002-02-01
FR0201213A FR2835519B1 (fr) 2002-02-01 2002-02-01 Procede bicomposant semi-continu d'obtention d'un chargement explosif composite a matrice polyurethanne

Publications (3)

Publication Number Publication Date
EP1333015A2 EP1333015A2 (fr) 2003-08-06
EP1333015A3 EP1333015A3 (fr) 2005-09-21
EP1333015B1 true EP1333015B1 (fr) 2009-11-04

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EP03290123A Expired - Lifetime EP1333015B1 (fr) 2002-02-01 2003-01-17 Procédé semi-continu d'obtention d'un chargement explosif composite à matrice polyuréthanne, ledit procédé mettant en oeuvre deux composants

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US (1) US6916390B2 (sl)
EP (1) EP1333015B1 (sl)
JP (1) JP3740128B2 (sl)
KR (1) KR100952063B1 (sl)
AT (1) ATE447545T1 (sl)
AU (1) AU2003200305B2 (sl)
BR (1) BR0300166B1 (sl)
CA (1) CA2418319C (sl)
DE (1) DE60329878D1 (sl)
DK (1) DK1333015T3 (sl)
ES (1) ES2333948T3 (sl)
FR (1) FR2835519B1 (sl)
IL (1) IL153983A (sl)
NO (1) NO329572B1 (sl)
PT (1) PT1333015E (sl)
SG (1) SG105568A1 (sl)
SI (1) SI1333015T1 (sl)
TW (1) TW593213B (sl)
ZA (1) ZA200300557B (sl)

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AU2006319000B2 (en) * 2005-11-24 2012-02-02 Eurenco Improved semi-continuous two-component method for obtaining a composite explosive charge with polyurethane-matrix

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FR2991317B1 (fr) 2012-06-04 2014-06-20 Eurenco France Explosif factice simulant un explosif malleable et son procede d'obtention
JP6115040B2 (ja) * 2012-08-22 2017-04-19 日油株式会社 炸薬組成物の製造方法及び該製造方法で製造した炸薬組成物
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GB2512346B (en) * 2013-03-27 2021-06-30 Bae Systems Plc Non-phthalate propellants
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GB2540159B (en) * 2015-07-07 2021-06-02 Bae Systems Plc PBX composition
FR3072676A1 (fr) * 2017-10-24 2019-04-26 Arianegroup Sas Procede de fabrication d'un produit pyrotechnique composite
US11766809B2 (en) * 2018-03-05 2023-09-26 Bae Systems Plc Method of forming pre-defined recess in cured or cast explosive composition
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AU2006319000B2 (en) * 2005-11-24 2012-02-02 Eurenco Improved semi-continuous two-component method for obtaining a composite explosive charge with polyurethane-matrix

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AU2003200305B2 (en) 2008-04-03
EP1333015A3 (fr) 2005-09-21
NO20030488D0 (no) 2003-01-30
KR20030066413A (ko) 2003-08-09
IL153983A0 (en) 2003-07-31
IL153983A (en) 2005-09-25
NO20030488L (no) 2003-08-04
JP2004035390A (ja) 2004-02-05
EP1333015A2 (fr) 2003-08-06
DK1333015T3 (da) 2010-03-22
SI1333015T1 (sl) 2010-02-26
CA2418319A1 (fr) 2003-08-01
JP3740128B2 (ja) 2006-02-01
FR2835519A1 (fr) 2003-08-08
US6916390B2 (en) 2005-07-12
BR0300166A (pt) 2003-09-09
SG105568A1 (en) 2004-08-27
BR0300166B1 (pt) 2013-10-01
FR2835519B1 (fr) 2004-11-19
KR100952063B1 (ko) 2010-04-13
ES2333948T3 (es) 2010-03-03
US20050115652A1 (en) 2005-06-02
TW593213B (en) 2004-06-21
AU2003200305A1 (en) 2003-08-21
PT1333015E (pt) 2010-02-02
TW200302815A (en) 2003-08-16
NO329572B1 (no) 2010-11-15
ZA200300557B (en) 2003-08-22
ATE447545T1 (de) 2009-11-15
CA2418319C (fr) 2008-11-04
DE60329878D1 (de) 2009-12-17

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