EP3114099A1 - Low-toxicity smoke pyrotechnic compositions for wide band masking - Google Patents

Low-toxicity smoke pyrotechnic compositions for wide band masking

Info

Publication number
EP3114099A1
EP3114099A1 EP15707643.1A EP15707643A EP3114099A1 EP 3114099 A1 EP3114099 A1 EP 3114099A1 EP 15707643 A EP15707643 A EP 15707643A EP 3114099 A1 EP3114099 A1 EP 3114099A1
Authority
EP
European Patent Office
Prior art keywords
composition
compound
polyaromatic
polyheteroaromatic
weight
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.)
Granted
Application number
EP15707643.1A
Other languages
German (de)
French (fr)
Other versions
EP3114099B1 (en
Inventor
Alexandrine Maraval
Loic BORDERIEUX
Dominique Medus
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.)
Etienne LaCroix Tous Artifices SA
Original Assignee
Etienne LaCroix Tous Artifices SA
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 Etienne LaCroix Tous Artifices SA filed Critical Etienne LaCroix Tous Artifices SA
Publication of EP3114099A1 publication Critical patent/EP3114099A1/en
Application granted granted Critical
Publication of EP3114099B1 publication Critical patent/EP3114099B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D3/00—Generation of smoke or mist (chemical part)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/02—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect
    • F42B12/36—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information
    • F42B12/46—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information for dispensing gases, vapours, powders or chemically-reactive substances
    • F42B12/48—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information for dispensing gases, vapours, powders or chemically-reactive substances smoke-producing, e.g. infrared clouds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B27/00—Hand grenades

Definitions

  • the present invention relates to low toxicity pyrotechnic compositions advantageously intended for the protection of terrestrial platforms (such as vehicles or armored vehicles), in particular against infrared-guided threats. Said compositions make it possible to produce an effective camouflage cloud in the visible and infra-red range.
  • the masking compositions currently used generally comprise an oxidizing / reducing pair, and a fuel compound (fuel). During combustion, the fuel makes it possible to generate particles of shape and size adapted to ensure effective masking in the visible and infra-red, in particular for the spectral window between 3 and 14 ⁇ .
  • These compositions comprise chlorinated compounds, such as CLONACIRE® (composition comprising a mixture of chlorinated naphthalenes with a degree of substitution greater than 3) or hexachloroethane. These play the role of either oxidant or product generating particles.
  • the threshold of the first lethal effects and the threshold of the irreversible effects associated with HC1 gas for 10 minutes of exposure are 1300 ppm (threshold of the first lethal effects, or 1937 mg / m 3 ), and 240 ppm (threshold of irreversible effects, or 358 mg / m 3 ).
  • brominated compounds in pyrotechnic compositions is already known, particularly for applications as a decoy for the protection of aerial targets against infrared-guided threats, without however addressing the problem of the toxicity of said compositions.
  • the effects sought in this case are generally not masking fumes but infra-red radiation imitating the engine radiation of the air platforms.
  • US Pat. Nos. 3,498,925 and 3,400,082 teach the use of metal or organometallic but non-halogenated compounds to reduce the toxicity of pyrotechnic compositions for visible masking.
  • the application US 2012/0267016 which relates to smoke compositions for visible masking, recommends the use of a mixture comprising melamine and polymethyl methylgallate.
  • these compositions comprise as sucrose fuel, and as oxidant a chlorate.
  • US Pat. No. 4,238,254 discloses pyrotechnic compositions for visible masking, including guanidine nitrate, which produces basic compounds capable of neutralizing the hydrogen chloride (HC1) or phosphorus pentoxide produced in the fumes.
  • HC1 hydrogen chloride
  • phosphorus pentoxide produced in the fumes.
  • the prior art therefore consistently teaches that, in order to reduce or even eliminate the toxicity of the pyrotechnic masking compositions, it is necessary to avoid any use of halogenated product, either
  • a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms significantly reduces the toxicity of the pyrotechnic compositions. compared to those of the prior art, while maintaining their masking performance both in the visible and in the infrared.
  • the term "spectral window" means a range of wavelengths.
  • polyaromatic is meant in the sense of the present invention a C10-C14 hydrocarbon compound, consisting of 2 to 3 contiguous aromatic rings. Examples of polyaromatic compounds that may be mentioned include naphthalene, anthracene and phenanthrene. Preferably, it is naphthalene and anthracene, more preferably naphthalene.
  • polyheteroaromatic compound is intended to mean a compound consisting of 2 to 3 aromatic or heteroaromatic fused rings and comprising at least one nitrogen heteroaromatic ring.
  • polyheteroaromatic compounds mention may be made especially of quinoline, isoquinoline and naphthyridine. Preferably, it is quinoline.
  • chlorinated compound means an organic compound comprising at least one chlorine atom, especially a compound comprising at least one carbon-chlorine (C-Cl) bond.
  • the present invention is directed exclusively to chemically stable compounds.
  • the polyaromatic or polyheteroaromatic compounds substituted with 1 to 3 bromine atoms according to the invention do not comprise chlorinated substituents.
  • the polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms has no further substituents.
  • the potentially toxic species emitted during the combustion of the fumigene are determined.
  • the quantities emitted during combustion are evaluated by thermodynamic calculation codes.
  • the thresholds of the first lethal effects and the thresholds of the irreversible effects are investigated in the literature. These two thresholds are evaluated according to the duration of exposure of the subject to the toxic substance, here HBr gas.
  • the threshold of the first lethal effects and the threshold of the irreversible effects associated at HBr gaseous for 10 minutes of exposure are 3290 ppm (threshold of the first lethal effects, or 11054 mg / m 3 ), and 366 ppm (threshold of irreversible effects, or 1228 mg / m 3 ).
  • the present invention therefore firstly relates to the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel in a pyrotechnic composition, preferably fumigant, so that, during the combustion of said composition , the toxic substance content of the emitted gases, such as hydrobromic acid, is less than 350 ppm, preferably less than 300 ppm.
  • the present invention also relates to a pyrotechnic composition, preferably a fumigant, comprising at least one reducing agent, a binder and at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel, and optionally an oxidizing agent, in the proportions following:
  • a fuel comprising at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
  • the present invention further relates to a pyrotechnic device comprising said composition.
  • the present invention also relates to a method of masking a target comprising the production of a smoke screen prohibiting the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably fumigant, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel.
  • a pyrotechnic composition preferably fumigant, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel.
  • the present invention therefore relates to the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as defined above as a fuel in a pyrotechnic composition, preferably fumigant, in which, during the combustion of said composition, the substance content toxic, especially hydrobromic acid, emitted gas is less than 350 ppm, preferably less than 300 ppm.
  • the combustion of said composition provides a camouflage coefficient in the spectral window 8 to 12 ⁇ greater than 50%, preferably greater than 60%, typically for 15 seconds, preferably for 20 seconds.
  • the combustion of said composition provides a camouflage coefficient in the spectral window 3 to 5 ⁇ greater than 60%>, preferably greater than 70%), typically for 15 seconds, preferably for 20 seconds.
  • camouflage coefficient means the ratio Cm (t) expressed as a percentage calculated at time t according to the following formula:
  • Nb (t) and Nb ' are the numerical levels respectively with and without effect on the hot source; Nn (t) and Nn 'are the digital levels respectively with and without effect on the cold source.
  • the camouflage coefficient is typically measured under controlled and reproducible conditions.
  • the measuring devices used are transmitting means such as:
  • a hot source of black-body type which has a temperature regulated around 200 ° C.
  • receiver measuring means such as:
  • the smoke composition does not contain any chlorinated compound.
  • the polyaromatic or polyheteroaromatic compound is substituted by 2 bromine atoms, even more advantageously it is a dibromonaphthalene or a dibromoquinoline, still more preferably 1,4-dibromonapthalene, 1,8-dibromoquinoline or 4,7-dibromoquinoline.
  • the present invention also relates to a pyrotechnic composition, preferably a fumigant, comprising at least one reducing agent, a binder and at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel, and optionally an oxidizing agent, in the proportions following:
  • a binder optionally mixed with a plasticizer, and 50 to 90% by weight, preferably 60 to 80% by weight, of a fuel comprising at least one polyaromatic compound or substituted polyheteroaromatic compound by 1 to 3 bromine atoms,
  • the weight of the binder is adjusted, if necessary, so that the percentages of the various elements added are worth 100%.
  • the percentage of binder is adjusted relative to the weight percentages of reducing agent, fuel, optionally oxidizing agent and additives, to obtain 100%.
  • the composition is free of chlorinated compound.
  • the polyaromatic or polyheteroaromatic compound is substituted with 2 bromine atoms.
  • the polyaromatic or polyheteroaromatic compound is substituted with 2 bromine atoms, even more advantageously it is a dibromonaphthalene or a dibromoquinoline, even more advantageously 1,4-dibromonapthalene, 1,8-dibromoquinoline. or 4,7-dibromoquinoline.
  • the reducing agent is chosen from magnesium, aluminum, zirconium, titanium, silicon and boron, or mixtures thereof, for example in the form of a metal powder.
  • the reducing agent consists essentially of magnesium powder or a mixture of zirconium and magnesium.
  • the binder also acts as an oxidizer.
  • the compositions do not comprise oxidant in addition to the binder.
  • the pyrotechnic composition, preferably fumigant, according to the invention preferably comprises:
  • a fuel comprising at least one polyaromatic compound or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
  • the binder is then chosen from fluoroelastomers or their mixtures, advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF), or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene (such as VITON®) or their mixtures.
  • fluoroelastomers or their mixtures advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF), or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene (such as VITON®) or their mixtures.
  • the binder does not act as an oxidizer.
  • the compositions according to the invention comprise between 5% and 15% by weight of oxidant, advantageously chosen from potassium chlorate, ammonium chlorate, potassium perchlorate and ammonium perchlorate. potassium nitrate or ammonium nitrate, or mixtures thereof.
  • the oxidant may also be chosen from fluoroelastomers or mixtures thereof, advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene. or their mixtures.
  • the binder is then chosen from phenolic polymers, epoxy resins and polybutadiene.
  • the oxidant is advantageously chosen from polytetrafluoroethylene, poly (carbon monofluoride) (PMF), or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or or tetrafluoroethylene or mixtures thereof.
  • the pyrotechnic composition preferably fumigant, according to the invention preferably comprises: 5 to 25%, preferably 10 to 20%, by weight of reducing agent,
  • a fuel comprising at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
  • compositions according to the invention may also comprise additives, such as hardeners, combustion retarders, flame inhibitors.
  • the combustion retarders are chosen in particular from diatoms and graphite carbon.
  • An example of a preferred flame inhibitor is sodium hydrogencarbonate.
  • Preferred additives are combustion retarders and flame inhibitors.
  • the present invention also relates to a pyrotechnic device comprising a container in which is housed the payload of pyrotechnic composition according to the invention.
  • the pyrotechnic composition according to the invention is shaped by compression.
  • the container is typically a smoke pot or a grenade capable of being thrown by a launcher or manually.
  • the present invention also relates to a method of masking a target comprising the production of a smoke screen prohibiting the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably fumigant, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel.
  • a pyrotechnic composition preferably fumigant, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel.
  • said pyrotechnic composition is as defined above.
  • Figure 1 curve representing the evolution of the camouflage coefficient for the optical window 3-5 ⁇ for composition 1.
  • the abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
  • Figure 2 curve representing the evolution of the camouflage coefficient for the optical window 8-12 ⁇ for composition 1.
  • the abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
  • Figure 3 curve representing the evolution of the camouflage coefficient for the optical window 3-5 ⁇ for the composition 2.
  • the abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
  • Figure 4 curve representing the evolution of the camouflage coefficient for the optical window 8-12 ⁇ for the composition 2.
  • the abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
  • thermodynamic calculation was carried out in the absence of oxygen from the air, under 2 atmospheres of pressure and at a temperature of 2000K.
  • the mass fractions of the species emitted from this calculation show mainly a toxic species which is HBr. Its mass fraction is given by the Coppelia calculation as being equal to 0.3436.
  • the maximum concentration near the source of the smoke that is to say the smoke pot burning HBr can be estimated at 300 ppm. This concentration decreases rapidly by dilution as soon as one moves away from this source. Thresholds of toxicity described in the literature for the HBr molecule:
  • compositions tested contain as fuel 1,4-dibromonaphthalene. It is this fuel which, combined with the reducing oxidizing couple, makes it possible to ensure broadband masking performance.
  • the binder used is a fluorinated polymer of Viton® type. This binder also serves as an oxidant in the composition.
  • the reducer used is magnesium.
  • the 1,4-dibromonaphthalene is present in the composition at about 70%, the Viton® binder is 11% by weight of the composition, the reducing agent constitutes 19% of the mixture.
  • the binder used is an epoxy resin associated with its hardener.
  • the oxidant used in the composition is a fluorinated polymer of polytetrafluoroethylene type.
  • the reducer used is magnesium.
  • a retarder of Combustion is also used in the composition, it is carbon graphite. 1,4-Dibromonaphthalene is present in this composition up to 68%, the binder up to 3%, the reducer up to 17%, the oxidizer up to 10% and the retarder combustion represents 2% in mass of the composition.
  • the compositions tested are compressed in the form of cylindrical smoke pots. The mass of composition contained in each pot is about 400g.
  • the test means makes it possible to move the smoke cloud at a controlled speed so as to pass it in a controlled and reproducible manner in front of the measuring means described below.
  • the measuring means consist of emitting sources which are:
  • a hot source of the blackbody type which has a temperature regulated around 200 ° C.
  • a cold source typically a steel plate at room temperature
  • Cm Camouflage coefficient (expressed as a percentage) calculated according to the following formula: in which
  • Nb (t) and Nb ' are the numerical levels respectively with and without effect on the hot source
  • Nn (t) and Nn ' are the digital levels respectively with and without effect on the cold source.
  • compositions 1 and 2 in the spectral windows 3-5 ⁇ and 8-12 ⁇ are shown in FIGS. 1 to 4.
  • composition 1 as well as for composition 2, the combustion of said composition offers a camouflage coefficient in the spectral window 8 to 12 ⁇ and 3-5 ⁇ greater than 50%, for at least 20 seconds.
  • composition 1 provides a camouflage coefficient greater than 70% for 15 seconds in the spectral band 3-5 ⁇ and greater than 60% for 15 seconds in the spectral window 8-12 ⁇ .
  • composition 2 provides a camouflage coefficient greater than 70%> for 30 seconds in the spectral band 3-5 ⁇ and greater than 60%> for 20 seconds in the spectral window 8-12 ⁇ .

Abstract

The present invention relates to smoke pyrotechnic compositions intended for protecting land platforms, in particular against infrared-guided threats. Said compositions include a polyaromatic or polyheteroaromatic compound substituted by 1 to 3 bromine atoms as fuel in a pyrotechnic composition, preferably a smoke pyrotechnic composition, such that, when said composition combusts, the toxic substance content of the emitted gases, such as hydrobromic acid, is less than 350 ppm, preferably less than 300 ppm.

Description

COMPOSITIONS PYROTECHNIQUES FUMIGENES DE MASQUAGE LARGE  LARGE FUMIGENATED PYROTECHNIC COMPOSITIONS
BANDE DE FAIBLE TOXICITE  BAND OF LOW TOXICITY
La présente invention concerne des compositions pyrotechniques de faible toxicité avantageusement destinées à la protection des plateformes terrestres (telles que des véhicules ou blindés), en particulier contre les menaces à guidée infrarouge. Lesdites compositions permettent de produire un nuage de camouflage efficace dans le domaine visible et infra-rouge. The present invention relates to low toxicity pyrotechnic compositions advantageously intended for the protection of terrestrial platforms (such as vehicles or armored vehicles), in particular against infrared-guided threats. Said compositions make it possible to produce an effective camouflage cloud in the visible and infra-red range.
Les compositions de masquage actuellement utilisées comprennent en général un couple oxydant/réducteur, et un composé servant de combustible (fuel). Lors de la combustion, le combustible permet de générer des particules de forme et de taille adaptée pour assurer un masquage efficace dans le visible et l'infra-rouge, en particulier pour la fenêtre spectrale comprise entre 3 et 14 μιη. Ces compositions comprennent des composés chlorés, tels la CLONACIRE® (composition comprenant un mélange de naphthalènes chlorés avec un taux de substitution supérieur à 3) ou Phexachloroéthane. Ceux-ci jouent le rôle soit d'oxydant, soit de produit générateur de particules. The masking compositions currently used generally comprise an oxidizing / reducing pair, and a fuel compound (fuel). During combustion, the fuel makes it possible to generate particles of shape and size adapted to ensure effective masking in the visible and infra-red, in particular for the spectral window between 3 and 14 μιη. These compositions comprise chlorinated compounds, such as CLONACIRE® (composition comprising a mixture of chlorinated naphthalenes with a degree of substitution greater than 3) or hexachloroethane. These play the role of either oxidant or product generating particles.
Cependant, ces composés fortement chlorés, lors de leur dégradation, forment des produits toxiques, en particulier du HC1 (acide chlorhydrique gazeux) en grande quantité. However, these highly chlorinated compounds, during their degradation, form toxic products, in particular HCl (gaseous hydrochloric acid) in large quantities.
Selon les évaluations du Ministère de l'Écologie et du Développement Durable, Ministère de la Santé, de la Famille et des Personnes Handicapées (Fiche INERIS, 2003), le seuil des premiers effets létaux et le seuil des effets irréversibles associés à HC1 gazeux pour 10 minutes d'exposition sont de 1300 ppm (seuil des premiers effets létaux, ou 1937 mg/m3), et de 240 ppm (seuil des effets irréversibles, ou 358 mg/m3). According to the assessments of the Ministry of Ecology and Sustainable Development, Ministry of Health, Family and People with Disabilities (INERIS Card, 2003), the threshold of the first lethal effects and the threshold of the irreversible effects associated with HC1 gas for 10 minutes of exposure are 1300 ppm (threshold of the first lethal effects, or 1937 mg / m 3 ), and 240 ppm (threshold of irreversible effects, or 358 mg / m 3 ).
Il existe donc un besoin pour des compositions pyrotechniques présentant de bonnes performances de masquage avec une faible toxicité. There is therefore a need for pyrotechnic compositions having good masking performance with low toxicity.
L'utilisation de composés bromés dans des compositions pyrotechniques est déjà connue, notamment pour des applications en tant que leurre pour la protection de cibles aériennes contre les menaces à guidée infrarouge, sans toutefois aborder le problème de la toxicité desdites compositions. Les effets recherchés dans ce cas ne sont généralement pas des fumées de masquage mais un rayonnement infra-rouge imitant le rayonnement du moteur des plateformes aériennes. The use of brominated compounds in pyrotechnic compositions is already known, particularly for applications as a decoy for the protection of aerial targets against infrared-guided threats, without however addressing the problem of the toxicity of said compositions. The effects sought in this case are generally not masking fumes but infra-red radiation imitating the engine radiation of the air platforms.
Par ailleurs, le brevet US 5,389,308, qui concerne des compositions générant des fumées opaques aux infrarouges comprenant de la poudre de magnésium, un polymère organique fluoré, de la chloroparaffïne et un composé aromatique, pouvant être un composé aromatique bromé tel le 8-bromoanthracène, enseigne que les composés non- halogénés sont préférés du fait de leur moindre toxicité. Furthermore, US Pat. No. 5,389,308, which relates to compositions generating infrared-opaque fumes comprising magnesium powder, an organic fluorinated polymer, chloroparaffin and an aromatic compound, which can be a brominated aromatic compound such as 8-bromoanthracene, teaches that non-halogenated compounds are preferred because of their lower toxicity.
De même, les brevets US 3,498,925 et US 3,400,082 enseignent l'utilisation de composés métalliques ou organométalliques mais non halogénés pour réduire la toxicité de compositions pyrotechniques pour masquage dans le visible. La demande US 2012/0267016, qui concerne des compositions fumigènes pour masquage dans le visible, préconise quant à elle l'utilisation d'un mélange comprenant de la mélamine et du méthylgallate polyméthylé. Par ailleurs, ces compositions comprennent comme combustible du sucrose, et comme oxydant un chlorate. En outre, le brevet US 4,238,254 décrit des compositions pyrotechniques pour masquage dans le visible, incluant du nitrate de guanidine, qui produit des composés basiques capables de neutraliser le chlorure d'hydrogène (HC1) ou de pentoxyde de phosphore produits dans les fumées. L'art antérieur enseigne donc de manière constante que, pour diminuer voire supprimer la toxicité des compositions pyrotechniques de masquage, il convient d'éviter toute utilisation de produit halogéné, aussi bien en tant qu'oxydant, réducteur ou combustible. Similarly, US Pat. Nos. 3,498,925 and 3,400,082 teach the use of metal or organometallic but non-halogenated compounds to reduce the toxicity of pyrotechnic compositions for visible masking. The application US 2012/0267016, which relates to smoke compositions for visible masking, recommends the use of a mixture comprising melamine and polymethyl methylgallate. Moreover, these compositions comprise as sucrose fuel, and as oxidant a chlorate. In addition, US Pat. No. 4,238,254 discloses pyrotechnic compositions for visible masking, including guanidine nitrate, which produces basic compounds capable of neutralizing the hydrogen chloride (HC1) or phosphorus pentoxide produced in the fumes. The prior art therefore consistently teaches that, in order to reduce or even eliminate the toxicity of the pyrotechnic masking compositions, it is necessary to avoid any use of halogenated product, either as an oxidant, a reducing agent or a fuel.
De manière surprenante, la demanderesse a cependant constaté que l'utilisation d'un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible dans une composition pyrotechnique, de préférence fumigène, permet de diminuer signifîcativement la toxicité des compositions pyrotechniques par rapport à celles de l'art antérieur, tout en conservant leur performance de masquage aussi bien dans le visible que dans l'infrarouge. Par « fenêtre spectrale », on entend au sens de la présente invention un domaine de longueur d'ondes. Par composé « polyaromatique » on entend au sens de la présente invention un composé hydrocarboné en C10 à C14, constitué de 2 à 3 cycles aromatiques accolés. On peut citer notamment comme exemple de composés polyaromatiques le naphthalène, l'anthracène et le phénanthrène. De préférence, il s'agit du naphthalène et de l'anthracène, de manière encore préférée du naphthalène. Surprisingly, the Applicant has found, however, that the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel in a pyrotechnic composition, preferably fumigant, significantly reduces the toxicity of the pyrotechnic compositions. compared to those of the prior art, while maintaining their masking performance both in the visible and in the infrared. For the purposes of the present invention, the term "spectral window" means a range of wavelengths. By "polyaromatic" compound is meant in the sense of the present invention a C10-C14 hydrocarbon compound, consisting of 2 to 3 contiguous aromatic rings. Examples of polyaromatic compounds that may be mentioned include naphthalene, anthracene and phenanthrene. Preferably, it is naphthalene and anthracene, more preferably naphthalene.
Par composé « polyhétéroaromatique » on entend au sens de la présente invention un composé constitué de 2 à 3 cycles aromatiques ou hétéroaromatiques accolés et comprenant au moins un cycle hétéroaromatique azoté. On peut citer notamment comme exemple de composés polyhétéroaromatique la quinoline, l'isoquinoline, naphthyridine. De préférence, il s'agit de la quinoline. For the purposes of the present invention, the term "polyheteroaromatic compound" is intended to mean a compound consisting of 2 to 3 aromatic or heteroaromatic fused rings and comprising at least one nitrogen heteroaromatic ring. As examples of polyheteroaromatic compounds, mention may be made especially of quinoline, isoquinoline and naphthyridine. Preferably, it is quinoline.
Par « composé chloré », on entend au sens de la présente invention un composé organique comprenant au moins un atome de chlore, notamment un composé comportant au moins une liaison carbone chlore (C-Cl). For the purpose of the present invention, the term "chlorinated compound" means an organic compound comprising at least one chlorine atom, especially a compound comprising at least one carbon-chlorine (C-Cl) bond.
La présente invention vise exclusivement les composés stables chimiquement. Avantageusement, les composés polyaromatiques ou polyhétéroaromatiques substitués par 1 à 3 atomes de brome selon l'invention ne comportent pas de substituants chlorés. The present invention is directed exclusively to chemically stable compounds. Advantageously, the polyaromatic or polyheteroaromatic compounds substituted with 1 to 3 bromine atoms according to the invention do not comprise chlorinated substituents.
De préférence, le composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome ne comporte pas d'autres substituants. Preferably, the polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms has no further substituents.
Pour déterminer la toxicité d'une composition pyrotechnique, les espèces potentiellement toxiques émises lors de la combustion du fumigène sont déterminées. Les quantités émises lors de la combustion sont évaluées par des codes de calcul thermodynamiques. Pour chaque espèce toxique identifiée, on recherche dans la littérature les seuils des premiers effets létaux et les seuils des effets irréversibles. Ces deux seuils sont évalués en fonction de la durée d'exposition du sujet à la substance toxique, ici HBr gazeux. To determine the toxicity of a pyrotechnic composition, the potentially toxic species emitted during the combustion of the fumigene are determined. The quantities emitted during combustion are evaluated by thermodynamic calculation codes. For each identified toxic species, the thresholds of the first lethal effects and the thresholds of the irreversible effects are investigated in the literature. These two thresholds are evaluated according to the duration of exposure of the subject to the toxic substance, here HBr gas.
Selon le rapport du Groupe d'Experts Toxicologues du Ministère de l'Ecologie, de l'Energie, du Développement Durable et de l'Aménagement du Territoire (15 avril 2008), le seuil des premiers effets létaux et le seuil des effets irréversibles associés à HBr gazeux pour 10 minutes d'exposition sont de 3290 ppm (seuil des premiers effets létaux, ou 11054 mg/m3), et de 366 ppm (seuil des effets irréversibles, ou 1228 mg/m3). La présente invention concerne donc en premier lieu l'utilisation d'un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible dans une composition pyrotechnique, de préférence fumigène, de manière que, lors de la combustion de ladite composition, la teneur en substance toxique des gaz émis, telle que l'acide bromhydrique, soit inférieure à 350 ppm, de préférence inférieure à 300 ppm. According to the report of the Group of Toxicological Experts of the Ministry of Ecology, Energy, Sustainable Development and Territorial Development (April 15, 2008), the threshold of the first lethal effects and the threshold of the irreversible effects associated at HBr gaseous for 10 minutes of exposure are 3290 ppm (threshold of the first lethal effects, or 11054 mg / m 3 ), and 366 ppm (threshold of irreversible effects, or 1228 mg / m 3 ). The present invention therefore firstly relates to the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel in a pyrotechnic composition, preferably fumigant, so that, during the combustion of said composition , the toxic substance content of the emitted gases, such as hydrobromic acid, is less than 350 ppm, preferably less than 300 ppm.
La présente invention concerne également une composition pyrotechnique, de préférence fumigène, comprenant au moins un réducteur, un liant et au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible, et éventuellement un oxydant, dans les proportions suivantes : The present invention also relates to a pyrotechnic composition, preferably a fumigant, comprising at least one reducing agent, a binder and at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel, and optionally an oxidizing agent, in the proportions following:
- 5 à 25 % en poids de réducteur,  5 to 25% by weight of reducing agent,
- 2 à 25 % en poids d'un liant, éventuellement en mélange avec un plastifiant, et 2 to 25% by weight of a binder, optionally mixed with a plasticizer, and
- 50 à 90 % en poids d'un combustible comprenant au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome, 50 to 90% by weight of a fuel comprising at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
- optionnellement 5% à 15% en poids d'oxydant,  optionally 5% to 15% by weight of oxidant,
- optionnellement de 2 à 10% en poids d'additifs  optionally from 2 to 10% by weight of additives
par rapport au poids total de la composition. relative to the total weight of the composition.
La présente invention concerne en outre un dispositif pyrotechnique comprenant ladite composition. The present invention further relates to a pyrotechnic device comprising said composition.
La présente invention concerne également un procédé de masquage d'une cible comprenant la production d'un écran de fumée interdisant la transmission du rayonnement infrarouge entre la cible et la menace à l'aide d'une composition pyrotechnique, de préférence fumigène, comprenant un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible. The present invention also relates to a method of masking a target comprising the production of a smoke screen prohibiting the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably fumigant, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel.
La présente invention a donc trait à l'utilisation d'un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome tel que défini précédemment en tant que combustible dans une composition pyrotechnique, de préférence fumigène, dans laquelle, lors de la combustion de ladite composition, la teneur en substance toxique, notamment l'acide bromhydrique, des gaz émis soit inférieure à 350 ppm, de préférence inférieure à 300 ppm. The present invention therefore relates to the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as defined above as a fuel in a pyrotechnic composition, preferably fumigant, in which, during the combustion of said composition, the substance content toxic, especially hydrobromic acid, emitted gas is less than 350 ppm, preferably less than 300 ppm.
Avantageusement, la combustion de ladite composition offre un coefficient de camouflage dans la fenêtre spectrale 8 à 12 μιη supérieur à 50%, de préférence supérieur à 60%, typiquement pendant 15 secondes, de préférence pendant 20 secondes. Avantageusement, la combustion de ladite composition offre un coefficient de camouflage dans la fenêtre spectrale 3 à 5 μιη supérieur à 60%>, de préférence supérieur à 70%), typiquement pendant 15 secondes, de préférence pendant 20 secondes. Advantageously, the combustion of said composition provides a camouflage coefficient in the spectral window 8 to 12 μιη greater than 50%, preferably greater than 60%, typically for 15 seconds, preferably for 20 seconds. Advantageously, the combustion of said composition provides a camouflage coefficient in the spectral window 3 to 5 μιη greater than 60%>, preferably greater than 70%), typically for 15 seconds, preferably for 20 seconds.
Par « coefficient de camouflage», on entend au sens de la présente invention le rapport Cm(t) exprimé en pourcentage calculé au temps t selon la formule suivante : For the purposes of the present invention, the term "camouflage coefficient" means the ratio Cm (t) expressed as a percentage calculated at time t according to the following formula:
dans laquelle in which
Nb(t) et Nb' sont les niveaux numériques respectivement avec et sans effet sur la source chaude ; Nn(t) et Nn' sont les niveaux numériques respectivement avec et sans effet sur la source froide. Nb (t) and Nb 'are the numerical levels respectively with and without effect on the hot source; Nn (t) and Nn 'are the digital levels respectively with and without effect on the cold source.
Le coefficient de camouflage est typiquement mesuré dans des conditions maîtrisées et reproductibles. Les appareils de mesure utilisés sont des moyens émetteurs tels que : The camouflage coefficient is typically measured under controlled and reproducible conditions. The measuring devices used are transmitting means such as:
- une source chaude de type corps noir qui présente une température régulée autour de 200°C, a hot source of black-body type which has a temperature regulated around 200 ° C.
- une source froide (typiquement une plaque d'acier à température ambiante). Et des moyens de mesure récepteurs tels que : a cold source (typically a steel plate at room temperature). And receiver measuring means such as:
- une caméra thermique travaillant en bande 2 (fenêtre spectrale 3-5 μιη) ; - a thermal camera working in band 2 (spectral window 3-5 μιη);
- une caméra thermique travaillant en bande 3 (fenêtre spectrale 8-12 μιη). De préférence, la composition fumigène ne contient pas de composé chloré. a thermal camera working in band 3 (spectral window 8-12 μιη). Preferably, the smoke composition does not contain any chlorinated compound.
Avantageusement, le composé polyaromatique ou polyhétéroaromatique est substitué par 2 atomes de brome, encore plus avantageusement, il s'agit d'un dibromonaphthalène ou d'une dibromoquinoline, encore plus avantageusement du 1 ,4-dibromonapthalène, de la 1 ,8- dibromoquinoline ou de la 4,7-dibromoquinoline. Advantageously, the polyaromatic or polyheteroaromatic compound is substituted by 2 bromine atoms, even more advantageously it is a dibromonaphthalene or a dibromoquinoline, still more preferably 1,4-dibromonapthalene, 1,8-dibromoquinoline or 4,7-dibromoquinoline.
La présente invention concerne également une composition pyrotechnique, de préférence fumigène, comprenant au moins un réducteur, un liant et au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible, et éventuellement un oxydant, dans les proportions suivantes : The present invention also relates to a pyrotechnic composition, preferably a fumigant, comprising at least one reducing agent, a binder and at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel, and optionally an oxidizing agent, in the proportions following:
- 5 à 25 % en poids, de préférence 10 à 20% en poids, de réducteur,  5 to 25% by weight, preferably 10 to 20% by weight, of reducing agent,
- 2 à 25 % en poids d'un liant, éventuellement en mélange avec un plastifiant, et - 50 à 90 % en poids, de préférence 60 à 80% en poids, d'un combustible comprenant au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome,  2 to 25% by weight of a binder, optionally mixed with a plasticizer, and 50 to 90% by weight, preferably 60 to 80% by weight, of a fuel comprising at least one polyaromatic compound or substituted polyheteroaromatic compound by 1 to 3 bromine atoms,
- optionnellement 5% à 15% en poids d'oxydant,  optionally 5% to 15% by weight of oxidant,
- optionnellement de 2 à 10% en poids d'additifs,  optionally from 2 to 10% by weight of additives,
par rapport au poids total de la composition. relative to the total weight of the composition.
Le poids du liant est ajusté, si besoin, de manière que les pourcentages des différents éléments additionnés valent 100%. Ainsi le pourcentage de liant est ajusté par rapport aux pourcentages massiques de réducteur, de combustible, optionnellement d'oxydant et d'additifs, pour obtenir 100%.  The weight of the binder is adjusted, if necessary, so that the percentages of the various elements added are worth 100%. Thus the percentage of binder is adjusted relative to the weight percentages of reducing agent, fuel, optionally oxidizing agent and additives, to obtain 100%.
De préférence, la composition est dépourvue de composé chloré. Preferably, the composition is free of chlorinated compound.
De préférence, le composé polyaromatique ou polyhétéroaromatique est substitué par 2 atomes de brome. Avantageusement, le composé polyaromatique ou polyhétéroaromatique est substitué par 2 atomes de brome, encore plus avantageusement, il s'agit d'un dibromonaphthalène ou d'une dibromoquinoline, encore plus avantageusement du 1 ,4-dibromonapthalène, de la 1 ,8- dibromoquinoline ou de la 4,7-dibromoquinoline.  Preferably, the polyaromatic or polyheteroaromatic compound is substituted with 2 bromine atoms. Advantageously, the polyaromatic or polyheteroaromatic compound is substituted with 2 bromine atoms, even more advantageously it is a dibromonaphthalene or a dibromoquinoline, even more advantageously 1,4-dibromonapthalene, 1,8-dibromoquinoline. or 4,7-dibromoquinoline.
Typiquement, le réducteur est choisi parmi le magnésium, l'aluminium, le zirconium, le titane, le silicium et le bore ou leurs mélanges, par exemple sous forme de poudre métallique. De préférence, le réducteur est essentiellement constitué de poudre de magnésium ou d'un mélange de zirconium et de magnésium.  Typically, the reducing agent is chosen from magnesium, aluminum, zirconium, titanium, silicon and boron, or mixtures thereof, for example in the form of a metal powder. Preferably, the reducing agent consists essentially of magnesium powder or a mixture of zirconium and magnesium.
Dans un premier mode de réalisation, le liant joue également le rôle d'oxydant. Dans ce mode de réalisation, les compositions ne comprennent pas d'oxydant en plus du liant. Dans ce premier mode de réalisation, la composition pyrotechnique, de préférence fumigène, selon l'invention comprend de préférence: In a first embodiment, the binder also acts as an oxidizer. In this embodiment, the compositions do not comprise oxidant in addition to the binder. In this first embodiment, the pyrotechnic composition, preferably fumigant, according to the invention preferably comprises:
- 5 à 25 % en poids de réducteur,  5 to 25% by weight of reducing agent,
- 5 à 25 % , de préférence de 10 à 15 %, en poids d'un liant, éventuellement en mélange avec un plastifiant, et  5 to 25%, preferably 10 to 15%, by weight of a binder, optionally mixed with a plasticizer, and
- 50 à 90 %, de préférence 60 à 70 %, en poids d'un combustible comprenant au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome,  - 50 to 90%, preferably 60 to 70%, by weight of a fuel comprising at least one polyaromatic compound or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
- optionnellement de 2 à 10% en poids d'additifs,  optionally from 2 to 10% by weight of additives,
par rapport au poids total de la composition. relative to the total weight of the composition.
Le liant est alors choisi parmi les fluoroélastomères ou leurs mélanges, avantageusement le polytetrafluoroéthylène, le poly (mono fluorure de carbone) (PMF, en anglais polycarbon mono fluoride) ou un copolymère de fluorure de vinylidène, hexafluoropropylène, perfluorométhylvinyléther et/ou tetrafluoroéthylène (tel le VITON®) ou leurs mélanges.  The binder is then chosen from fluoroelastomers or their mixtures, advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF), or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene (such as VITON®) or their mixtures.
Dans un second mode de réalisation, le liant ne joue pas le rôle d'oxydant. Dans ce mode de réalisation, les compositions selon l'invention comprennent entre 5% et 15% en poids d'oxydant, avantageusement choisi parmi le chlorate de potassium, le chlorate d'ammonium, le perchlorate de potassium, le perchlorate d'ammonium, le nitrate de potassium ou le nitrate d'ammonium, ou leurs mélanges. L'oxydant peut également être choisi parmi les fluoroélastomères ou leurs mélanges, avantageusement le polytetrafluoroéthylène, le poly(mono fluorure de carbone) (PMF, en anglais polycarbon mono fluoride) ou un copolymère de fluorure de vinylidène, hexafluoropropylène, perfluorométhylvinyléther et/ou tetrafluoroéthylène ou leurs mélanges.  In a second embodiment, the binder does not act as an oxidizer. In this embodiment, the compositions according to the invention comprise between 5% and 15% by weight of oxidant, advantageously chosen from potassium chlorate, ammonium chlorate, potassium perchlorate and ammonium perchlorate. potassium nitrate or ammonium nitrate, or mixtures thereof. The oxidant may also be chosen from fluoroelastomers or mixtures thereof, advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene. or their mixtures.
Le liant est alors choisi parmi les polymères phénoliques, les résines époxy et le polybutadiène. En particulier, lorsque le liant est une résine époxy, l'oxydant est avantageusement choisi parmi le polytetrafluoroéthylène, le poly(monofluorure de carbone) (PMF, en anglais polycarbon mono fluoride) ou un copolymère de fluorure de vinylidène, hexafluoropropylène, perfluorométhylvinyléther et/ou tetrafluoroéthylène ou leurs mélanges. The binder is then chosen from phenolic polymers, epoxy resins and polybutadiene. In particular, when the binder is an epoxy resin, the oxidant is advantageously chosen from polytetrafluoroethylene, poly (carbon monofluoride) (PMF), or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or or tetrafluoroethylene or mixtures thereof.
Dans ce second mode de réalisation, la composition pyrotechnique, de préférence fumigène, selon l'invention comprend de préférence: - 5 à 25 %, de préférence de 10 à 20%, en poids de réducteur,In this second embodiment, the pyrotechnic composition, preferably fumigant, according to the invention preferably comprises: 5 to 25%, preferably 10 to 20%, by weight of reducing agent,
- 2 à 10 %, de préférence de 3 à 5%, en poids d'un liant, éventuellement en mélange avec un plastifiant, 2 to 10%, preferably 3 to 5%, by weight of a binder, optionally mixed with a plasticizer,
- 5 à 15 %, de préférence de 10 à 15%, en poids d'oxydant et  5 to 15%, preferably 10 to 15%, by weight of oxidizing agent and
- 50 à 90 %>, de préférence 60 à 80 %>, en poids d'un combustible comprenant au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome,  50 to 90%, preferably 60 to 80%, by weight of a fuel comprising at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
- optionnellement de 2 à 10%> en poids d'additifs,  optionally from 2 to 10% by weight of additives,
par rapport au poids total de la composition. relative to the total weight of the composition.
Les compositions selon l'invention peuvent également comprendre des additifs, tels que des durcisseurs, des ralentisseurs de combustion, des inhibiteurs de flamme. Les ralentisseurs de combustion sont notamment choisis parmi les diatomées et le carbone graphite. Un exemple d'inhibiteur de flamme préféré est l'hydrogénocarbonate de sodium. Les additifs préférés sont les ralentisseurs de combustion et les inhibiteurs de flamme. The compositions according to the invention may also comprise additives, such as hardeners, combustion retarders, flame inhibitors. The combustion retarders are chosen in particular from diatoms and graphite carbon. An example of a preferred flame inhibitor is sodium hydrogencarbonate. Preferred additives are combustion retarders and flame inhibitors.
La présente invention vise également un dispositif pyrotechnique comprenant un conteneur dans lequel est logée la charge utile de composition pyrotechnique selon l'invention. De préférence, la composition pyrotechnique selon l'invention est mise en forme par compression. Le conteneur est typiquement un pot fumigène ou une grenade apte à être lancé(e) par un lanceur ou manuellement.  The present invention also relates to a pyrotechnic device comprising a container in which is housed the payload of pyrotechnic composition according to the invention. Preferably, the pyrotechnic composition according to the invention is shaped by compression. The container is typically a smoke pot or a grenade capable of being thrown by a launcher or manually.
La présente invention a également trait à un procédé de masquage d'une cible comprenant la production d'un écran de fumée interdisant la transmission du rayonnement infrarouge entre la cible et la menace à l'aide d'une composition pyrotechnique, de préférence fumigène, comprenant un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible. Avantageusement, ladite composition pyrotechnique est telle que définie ci-dessus. DESCRIPTION DES FIGURES The present invention also relates to a method of masking a target comprising the production of a smoke screen prohibiting the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably fumigant, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel. Advantageously, said pyrotechnic composition is as defined above. DESCRIPTION OF THE FIGURES
Figure 1 : courbe représentant l'évolution du coefficient de camouflage pour la fenêtre optique 3-5 μιη pour la composition 1. L'axe des abscisses représente le temps en secondes, l'axe des ordonnées représente le coefficient de camouflage en %. Figure 1: curve representing the evolution of the camouflage coefficient for the optical window 3-5 μιη for composition 1. The abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
Figure 2 : courbe représentant l'évolution du coefficient de camouflage pour la fenêtre optique 8-12 μιη pour la composition 1. L'axe des abscisses représente le temps en secondes, l'axe des ordonnées représente le coefficient de camouflage en %. Figure 2: curve representing the evolution of the camouflage coefficient for the optical window 8-12 μιη for composition 1. The abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
Figure 3 : courbe représentant l'évolution du coefficient de camouflage pour la fenêtre optique 3-5 μιη pour la composition 2. L'axe des abscisses représente le temps en secondes, l'axe des ordonnées représente le coefficient de camouflage en %. Figure 3: curve representing the evolution of the camouflage coefficient for the optical window 3-5 μιη for the composition 2. The abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
Figure 4 : courbe représentant l'évolution du coefficient de camouflage pour la fenêtre optique 8-12 μιη pour la composition 2. L'axe des abscisses représente le temps en secondes, l'axe des ordonnées représente le coefficient de camouflage en %. Figure 4: curve representing the evolution of the camouflage coefficient for the optical window 8-12 μιη for the composition 2. The abscissa axis represents the time in seconds, the ordinate axis represents the camouflage coefficient in%.
EXEMPLES EXAMPLES
Les exemples qui suivent sont donnés à titre illustratif, mais ne doivent en aucun cas être considérés comme limitatifs de la présente invention. The following examples are given for illustrative purposes, but should in no way be considered as limiting the present invention.
Exemple 1 : évaluation de la toxicité Example 1: Evaluation of toxicity
L'enthalpie de formation du 1 ,4-dibromonaphthalène a été définie comme étant égale à 27,6 kCal/mol à l'aide du logiciel Hyperchem et des données de la littérature. The formation enthalpy of 1,4-dibromonaphthalene was defined as 27.6 kCal / mol using Hyperchem software and literature data.
Une simulation de la combustion du 1 ,4-dibromonaphthalène permettant de déterminer les espèces émises lors de la combustion a été réalisée avec le logiciel Coppelia. Le calcul thermodynamique a été réalisé en absence d'oxygène de l'air, sous 2 atmosphères de pression et à une température de 2000K. Les fractions massiques des espèces émises issues de ce calcul font apparaître principalement une espèce toxique qui est le HBr. Sa fraction massique est donnée par le calcul Coppelia comme étant égale à 0,3436. A simulation of the combustion of 1,4-dibromonaphthalene to determine the species emitted during combustion was performed with Coppelia software. The thermodynamic calculation was carried out in the absence of oxygen from the air, under 2 atmospheres of pressure and at a temperature of 2000K. The mass fractions of the species emitted from this calculation show mainly a toxic species which is HBr. Its mass fraction is given by the Coppelia calculation as being equal to 0.3436.
A partir de ce résultat, la concentration maximale à proximité de la source de la fumée, c'est-à-dire du pot fumigène en combustion en HBr peut être estimée à 300 ppm. Cette concentration diminue rapidement par dilution dès qu'on s'éloigne de cette source. Seuils de toxicité décrits dans la littérature pour la molécule HBr : From this result, the maximum concentration near the source of the smoke, that is to say the smoke pot burning HBr can be estimated at 300 ppm. This concentration decreases rapidly by dilution as soon as one moves away from this source. Thresholds of toxicity described in the literature for the HBr molecule:
Les données disponibles concernant HBr gazeux (rapport du Groupe d'Experts Toxicologues du Ministère de l'Ecologie, de l'Energie, du Développement Durable et de l'Aménagement du Territoire du 15 avril 2008) décrivent les seuils des premiers effets létaux et les seuils des effets irréversibles associés à des temps d'exposition. Available data on gaseous HBr (report of the Group of Toxicological Experts of the Ministry of Ecology, Energy, Sustainable Development and Territorial Development of April 15, 2008) describe the thresholds of the first lethal effects and the thresholds for irreversible effects associated with exposure times.
Exemple 2 : évaluation des performances de masquage Example 2: Evaluating Masking Performance
Description des compositions testées : Description of the compositions tested:
Les compositions testées contiennent comme combustible le 1,4-dibromonaphthalène. C'est ce combustible qui, associé au couple oxydant réducteur, permet d'assurer la performance de masquage large bande. The compositions tested contain as fuel 1,4-dibromonaphthalene. It is this fuel which, combined with the reducing oxidizing couple, makes it possible to ensure broadband masking performance.
Dans le cas de la composition 1, le liant utilisé est un polymère fluoré de type Viton®. Ce liant sert également d'oxydant dans la composition. Le réducteur utilisé est du magnésium. Le 1,4-dibromonaphthalène est présent dans la composition à hauteur de 70% environ, le liant Viton® représente 11%> en masse de la composition, le réducteur constitue 19%> du mélange. In the case of composition 1, the binder used is a fluorinated polymer of Viton® type. This binder also serves as an oxidant in the composition. The reducer used is magnesium. The 1,4-dibromonaphthalene is present in the composition at about 70%, the Viton® binder is 11% by weight of the composition, the reducing agent constitutes 19% of the mixture.
Dans le cas de la composition 2, le liant utilisé est une résine époxy associée à son durcisseur. L'oxydant utilisé dans la composition est un polymère fluoré de type polytetrafluoroéthylène. Le réducteur utilisé est le magnésium. Un ralentisseur de combustion est également utilisé dans la composition, il s'agit de carbone graphite. Le 1 ,4-dibromonaphtalène est présent dans cette composition à hauteur de 68%, le liant à hauteur de 3%, le réducteur à hauteur de 17%, l'oxydant à hauteur de 10%> et le ralentisseur de combustion représente 2% en masse de la composition. Les compositions testées sont comprimées sous la forme de pots fumigènes cylindriques. La masse de composition contenue dans chaque pot est d'environ 400g. In the case of composition 2, the binder used is an epoxy resin associated with its hardener. The oxidant used in the composition is a fluorinated polymer of polytetrafluoroethylene type. The reducer used is magnesium. A retarder of Combustion is also used in the composition, it is carbon graphite. 1,4-Dibromonaphthalene is present in this composition up to 68%, the binder up to 3%, the reducer up to 17%, the oxidizer up to 10% and the retarder combustion represents 2% in mass of the composition. The compositions tested are compressed in the form of cylindrical smoke pots. The mass of composition contained in each pot is about 400g.
Description du moyen d'essai : Description of the test medium:
Le moyen d'essai permet de déplacer le nuage de fumée à une vitesse contrôlée de façon à le faire passer de façon maîtrisée et reproductible devant les moyens de mesure décrits ci-dessous. The test means makes it possible to move the smoke cloud at a controlled speed so as to pass it in a controlled and reproducible manner in front of the measuring means described below.
Description des moyens de mesure : Description of the measuring means:
Les moyens de mesures sont constitués de sources émettrices qui sont : The measuring means consist of emitting sources which are:
- une source chaude de type corps noir qui présente une température régulée autour de 200°C, - une source froide (typiquement une plaque d'acier à température ambiante). a hot source of the blackbody type which has a temperature regulated around 200 ° C., a cold source (typically a steel plate at room temperature).
Et de moyens de mesures récepteurs positionnés en vis-à-vis des sources qui sont : And receiving measurement means positioned in relation to the sources which are:
- une caméra thermique travaillant en bande 2 (fenêtre spectrale 3-5 μιη) - a thermal camera working in band 2 (spectral window 3-5 μιη)
- une caméra thermique travaillant en bande 3 (fenêtre spectrale 8-12 μιη). a thermal camera working in band 3 (spectral window 8-12 μιη).
Description de la mise en œuyre du pot fumigène : Le rideau de fumée se déplace et passe devant les moyens de mesure permettant ainsi de mesurer les performances infrarouge du fumigène dans des conditions maîtrisées et reproductibles. Description of the setting of the smoke pot: The smoke curtain moves and passes in front of the measurement means thus making it possible to measure the infrared performance of the smoke generator under controlled and reproducible conditions.
Description de la méthode de dépouillement des données : Description of the method of data analysis:
Pour chaque pot testé on calcule les valeurs suivantes à partir des enregistrements de la luminance obtenus avec les caméras thermiques bande 2 et bande 3. For each test pot the following values are calculated from the luminance recordings obtained with the band 2 and band 3 thermal cameras.
Cm = Coefficient de camouflage (exprimé en pourcentage) calculé selon la formule suivante : dans laquelle Cm = Camouflage coefficient (expressed as a percentage) calculated according to the following formula: in which
Nb(t) et Nb' sont les niveaux numériques respectivement avec et sans effet sur la source chaude ; Nb (t) and Nb 'are the numerical levels respectively with and without effect on the hot source;
Nn(t) et Nn' sont les niveaux numériques respectivement avec et sans effet sur la source froide. Nn (t) and Nn 'are the digital levels respectively with and without effect on the cold source.
Les résultats obtenus pour les compositions 1 et 2 dans les fenêtres spectrales 3-5 μιη et 8-12 μιη sont représentés sur les figures 1 à 4. The results obtained for compositions 1 and 2 in the spectral windows 3-5 μιη and 8-12 μιη are shown in FIGS. 1 to 4.
On constate que, aussi bien pour la composition 1 que pour la composition 2, la combustion de ladite composition offre un coefficient de camouflage dans la fenêtre spectrale 8 à 12 μιη et 3-5 μιη supérieur à 50%, pendant au moins 20 secondes. It can be seen that, for composition 1 as well as for composition 2, the combustion of said composition offers a camouflage coefficient in the spectral window 8 to 12 μιη and 3-5 μιη greater than 50%, for at least 20 seconds.
Plus précisément, la composition 1 offre un coefficient de camouflage supérieur à 70 % pendant 15 secondes dans la bande spectrale 3-5 μιη et supérieur à 60% pendant 15 secondes dans la fenêtre spectrale 8-12 μιη. Specifically, the composition 1 provides a camouflage coefficient greater than 70% for 15 seconds in the spectral band 3-5 μιη and greater than 60% for 15 seconds in the spectral window 8-12 μιη.
La composition 2 assure un coefficient de camouflage supérieur à 70%> pendant 30 secondes dans la bande spectrale 3-5 μιη et supérieur à 60%> pendant 20 secondes dans la fenêtre spectrale 8-12 μιη. The composition 2 provides a camouflage coefficient greater than 70%> for 30 seconds in the spectral band 3-5 μιη and greater than 60%> for 20 seconds in the spectral window 8-12 μιη.

Claims

REVENDICATIONS
1. Utilisation d'un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible dans une composition pyrotechnique, de préférence fumigène, dans laquelle, lors de la combustion de ladite composition, la teneur en substance toxique, telle que l'acide bromhydrique, des gaz émis soit inférieure à 400 ppm, de préférence inférieure à 350 ppm. 1. Use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel in a pyrotechnic composition, preferably fumigant, in which, during the combustion of said composition, the content of toxic substance, such as hydrobromic acid, emitted gases is less than 400 ppm, preferably less than 350 ppm.
2. Utilisation selon la revendication 1, caractérisée en ce que la combustion de ladite composition offre un coefficient de camouflage dans la fenêtre spectrale 8 à 12 μιη supérieur à 50%, de préférence supérieur à 60%, typiquement pendant 15 secondes. 2. Use according to claim 1, characterized in that the combustion of said composition provides a camouflage coefficient in the spectral window 8 to 12 μιη greater than 50%, preferably greater than 60%, typically for 15 seconds.
3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que la combustion de ladite composition offre un coefficient de camouflage dans la fenêtre spectrale 3 à 5 μιη supérieur à 60%>, de préférence supérieur à 70%>, typiquement pendant 15 secondes. 3. Use according to claim 1 or 2, characterized in that the combustion of said composition provides a camouflage coefficient in the spectral window 3 to 5 μιη greater than 60%>, preferably greater than 70%>, typically for 15 seconds .
4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la composition fumigène ne contient pas de composé chloré. 4. Use according to any one of claims 1 to 3, characterized in that the smoke composition does not contain chlorinated compound.
5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le composé polyaromatique ou polyhétéroaromatique est substitué par 2 atomes de brome. 5. Use according to any one of claims 1 to 4, characterized in that the polyaromatic compound or polyheteroaromatic compound is substituted with 2 bromine atoms.
6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le composé polyaromatique ou polyhétéroaromatique est un dibromonapthalène, ou une dibromoquinoline. 6. Use according to any one of claims 1 to 5, characterized in that the polyaromatic compound or polyheteroaromatic is a dibromonapthalene, or a dibromoquinoline.
7. Composition pyrotechnique, de préférence fumigène, comprenant au moins un réducteur, un liant et au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible, et éventuellement un oxydant, dans les proportions suivantes : Pyrotechnic composition, preferably fumigant, comprising at least one reducing agent, a binder and at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as a fuel, and optionally an oxidizing agent, in the following proportions:
- 5 à 25 % en poids de réducteur,  5 to 25% by weight of reducing agent,
- 2 à 25 % en poids d'un liant, éventuellement en mélange avec un plastifiant, et - 50 à 90 % en poids d'un combustible comprenant au moins un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome, 2 to 25% by weight of a binder, optionally mixed with a plasticizer, and 50 to 90% by weight of a fuel comprising at least one polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms,
- optionnellement 5% à 15% en poids d'oxydant, et  optionally 5% to 15% by weight of oxidant, and
- optionnellement de 2 à 10% en poids d'additifs  optionally from 2 to 10% by weight of additives
par rapport au poids total de la composition. relative to the total weight of the composition.
8. Composition selon la revendication 7, caractérisée en ce qu'elle ne contient pas de composé chloré. 8. Composition according to claim 7, characterized in that it does not contain chlorinated compound.
9. Composition selon la revendication 7 ou 8, caractérisée en ce que le composé polyaromatique ou polyhétéroaromatique est substitué par 2 atomes de brome. 9. Composition according to claim 7 or 8, characterized in that the polyaromatic or polyheteroaromatic compound is substituted with 2 bromine atoms.
10. Composition selon l'une quelconque des revendications 7 à 9, caractérisée en ce que le composé polyaromatique ou polyhétéroaromatique est un dibromonapthalène ou une dibromoquinoline. 10. Composition according to any one of claims 7 to 9, characterized in that the polyaromatic compound or polyheteroaromatic is a dibromonapthalene or a dibromoquinoline.
11. Composition selon l'une quelconque des revendications 7 à 10, caractérisée en ce que le réducteur est choisi parmi le magnésium, l'aluminium, le zirconium, le titane, le silicium et le bore ou leurs mélanges, par exemple sous forme de poudre métallique, de préférence le réducteur est essentiellement constitué de poudre de magnésium ou d'un mélange de zirconium et de magnésium. 11. Composition according to any one of claims 7 to 10, characterized in that the reducing agent is selected from magnesium, aluminum, zirconium, titanium, silicon and boron or mixtures thereof, for example in the form of metal powder, preferably the reducing agent consists essentially of magnesium powder or a mixture of zirconium and magnesium.
12. Composition selon l'une quelconque des revendications 7 à 11, caractérisée en ce que l'oxydant est choisi parmi le chlorate de potassium, le chlorate d'ammonium, le perchlorate de potassium, le perchlorate d'ammonium, le nitrate de potassium ou le nitrate d'ammonium, les fluoroélastomères, ou leurs mélanges. 12. Composition according to any one of claims 7 to 11, characterized in that the oxidant is selected from potassium chlorate, ammonium chlorate, potassium perchlorate, ammonium perchlorate, potassium nitrate. or ammonium nitrate, fluoroelastomers, or mixtures thereof.
13. Composition selon la revendication 12, caractérisée en ce que le liant est choisi parmi les polymères phénoliques, les résines époxy et le polybutadiène. 13. Composition according to claim 12, characterized in that the binder is chosen from phenolic polymers, epoxy resins and polybutadiene.
14. Composition selon l'une quelconque des revendications 7 à 11, caractérisée en ce que le liant joue également le rôle d'oxydant, et est avantageusement choisi parmi les fluoroélastomères, avantageusement le polytetrafluoroéthylène, le poly(mo no fluorure de carbone) ou un copolymère de fluorure de vinylidène, hexafluoropropylène, perfluorométhylvinyléther et/ou tetrafluoroéthylène, ou leurs mélanges. 14. Composition according to any one of claims 7 to 11, characterized in that the binder also acts as an oxidizer, and is advantageously chosen from the fluoroelastomers, advantageously polytetrafluoroethylene, poly (carbon mon fluoride) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene, or mixtures thereof.
15. Dispositif pyrotechnique comprenant un conteneur, typiquement un pot fumigène ou une grenade apte à être lancé(e) par un lanceur ou manuellement, dans lequel est logée la charge utile de composition pyrotechnique selon l'une quelconque des revendications 7 à 14. 15. Pyrotechnic device comprising a container, typically a smoke pot or a grenade capable of being launched by a launcher or manually, in which is housed the pyrotechnic composition payload according to any one of claims 7 to 14.
16. Procédé de masquage d'une cible comprenant la production d'un écran de fumée interdisant la transmission du rayonnement infrarouge entre la cible et la menace à l'aide d'une composition pyrotechnique, de préférence fumigène, comprenant un composé polyaromatique ou polyhétéroaromatique substitué par 1 à 3 atomes de brome en tant que combustible, de préférence ladite composition pyrotechnique est telle que définie dans l'une quelconque des revendications 7 à 14. 16. A method of masking a target comprising the production of a smoke screen prohibiting the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably fumigant, comprising a polyaromatic compound or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as fuel, preferably said pyrotechnic composition is as defined in any one of claims 7 to 14.
EP15707643.1A 2014-03-03 2015-03-03 Low-toxicity smoke pyrotechnic compositions for wide band masking Active EP3114099B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1451689A FR3018073B1 (en) 2014-03-03 2014-03-03 WET-BAND LOW-BAND SMOKING MASK FUNGICY PYROTECHNIC COMPOSITIONS WITH LOW TOXICITY
PCT/EP2015/054432 WO2015132266A1 (en) 2014-03-03 2015-03-03 Low-toxicity smoke pyrotechnic compositions for wide band masking

Publications (2)

Publication Number Publication Date
EP3114099A1 true EP3114099A1 (en) 2017-01-11
EP3114099B1 EP3114099B1 (en) 2021-05-26

Family

ID=52462333

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15707643.1A Active EP3114099B1 (en) 2014-03-03 2015-03-03 Low-toxicity smoke pyrotechnic compositions for wide band masking

Country Status (5)

Country Link
EP (1) EP3114099B1 (en)
KR (1) KR102325489B1 (en)
ES (1) ES2883403T3 (en)
FR (1) FR3018073B1 (en)
WO (1) WO2015132266A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1025879B1 (en) * 2018-01-08 2019-08-06 Mecar Sa Use of a halogenated salt of tetraphenyl phosphonium as a fumigant and fumigant pyrotechnic composition incorporating such material
KR102481792B1 (en) * 2021-07-14 2022-12-27 엘아이지넥스원 주식회사 Underwater installation structure hiding device and its control method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4096005A (en) * 1977-06-13 1978-06-20 Nuclei Engineering, Inc. Pyrotechnic cloud seeding composition
DE2819850C2 (en) * 1978-05-05 1980-03-20 Buck Chemisch-Technische Werke Gmbh & Co, 8230 Bad Reichenhall Pyrotechnic smoke kit
FR2560186B1 (en) * 1982-07-27 1987-06-05 France Etat Armement PYROTECHNIC COMPOSITION GENERATING OPAQUE SMOKE WITH INFRARED RADIATION AND FUMIGENE AMMUNITION OBTAINED
DE4030430C1 (en) * 1990-09-26 1993-12-02 Buck Chem Tech Werke Compsn. for generating IR-opaque smoke, esp. for camouflage - contains magnesium@ powder, fluoro:polymer, chloro:paraffin and aromatic cpd., esp. anthracene, phthalic anhydride, 2-benzoyl-pyridine etc.
DE102006030679A1 (en) 2006-07-04 2008-01-10 Diehl Bgt Defence Gmbh & Co. Kg Pyrotechnic set

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015132266A1 *

Also Published As

Publication number Publication date
KR20170007244A (en) 2017-01-18
FR3018073A1 (en) 2015-09-04
EP3114099B1 (en) 2021-05-26
ES2883403T3 (en) 2021-12-07
FR3018073B1 (en) 2016-04-01
WO2015132266A1 (en) 2015-09-11
KR102325489B1 (en) 2021-11-11

Similar Documents

Publication Publication Date Title
CA1243210A (en) Process for screening visible and infrared radiation and smoke generating round used therewith
CA1243209A (en) Dense smoke generating pyrotechnic composition capable of screening impated radiation and round incorporating same
EP3114099B1 (en) Low-toxicity smoke pyrotechnic compositions for wide band masking
Sabatini et al. High‐Nitrogen‐based pyrotechnics: development of perchlorate‐free green‐light illuminants for military and civilian applications
Koch et al. Metal‐fluorocarbon pyrolants. XIII: high performance infrared decoy flare compositions based on MgB2 and Mg2Si and Polytetrafluoroethylene/Viton®
CA1271334A (en) Pourable smoke-generating compounds highly efficient in ir
US6635130B2 (en) Pyrotechnic composition for producing IR-radiation
JPH08501268A (en) Castable infrared emitting composition
RU2369589C2 (en) Pyrotechnical smoke-generating composition
BE1025879B1 (en) Use of a halogenated salt of tetraphenyl phosphonium as a fumigant and fumigant pyrotechnic composition incorporating such material
US11414360B2 (en) Efficient smoke composition in visible and infrared ranges
Ruesch et al. Characterization of aluminum-lithium composite-propellant flames via laser absorption spectroscopy
US8608879B1 (en) Environmentally friendly flare illuminant composition
RU2462442C1 (en) Pyrotechnic smoke-producing composition
Iorga et al. Research Regarding the Properties and Combustion Performance of a Thermal Decoy Pyrotechnic Composition
WO2018183523A1 (en) Obscurant compositions
RU2326815C1 (en) Aerosol-forming compound
Nacu Practical aspects on using polytetrafluorethylene (PTFE) in pyrotechnic compositions
RU2542312C1 (en) Ignition composition for electric igniters and method of obtaining thereof
Zhang et al. Study on anti-infrared performance of organohalogen polymer smoke agent
RU2630559C2 (en) Injection moulding pyrotechnical composition for generation of smoke
EP0299835A1 (en) Pyrotechnical composition for the production of smoke opaque to infrared rays, process for its manufacture and decoy comprising such a composition
Webb et al. Technical Feasibility Study of an Effective Low-Toxicity Obscurant Material
Koch et al. Metal Fluorocarbon Pyrolants, XVI: Theoretical and Experimental Investigation of Poly [bis (2, 2, 2‐trifluoroethoxy) phosphazene](PTFEP) as Oxidizer in Magnesium Based Pyrolants

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20160915

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20181220

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201217

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

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

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015069672

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1396098

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20210526

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1396098

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210526

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: 20210826

Ref country code: AT

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: 20210526

Ref country code: HR

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: 20210526

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: 20210526

Ref country code: LT

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: 20210526

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

Ref country code: LV

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: 20210526

Ref country code: IS

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: 20210926

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: 20210827

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: 20210526

Ref country code: RS

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: 20210526

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: 20210927

Ref country code: PL

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: 20210526

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2883403

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20211207

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

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: 20210526

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: 20210526

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: 20210526

Ref country code: SM

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: 20210526

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: 20210526

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: 20210526

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015069672

Country of ref document: DE

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: 20220301

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

Ref country code: IS

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: 20210926

Ref country code: AL

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: 20210526

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

Ref country code: MC

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: 20210526

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LU

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

Effective date: 20220303

Ref country code: LI

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

Effective date: 20220331

Ref country code: IE

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

Effective date: 20220303

Ref country code: CH

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

Effective date: 20220331

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

Ref country code: NL

Payment date: 20230227

Year of fee payment: 9

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: 20220331

Ref country code: CH

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

Effective date: 20220331

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

Ref country code: NO

Payment date: 20230223

Year of fee payment: 9

Ref country code: FR

Payment date: 20230320

Year of fee payment: 9

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: LI

Effective date: 20230331

Ref country code: CH

Effective date: 20230331

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

Ref country code: IT

Payment date: 20230309

Year of fee payment: 9

Ref country code: GB

Payment date: 20230324

Year of fee payment: 9

Ref country code: DE

Payment date: 20230307

Year of fee payment: 9

Ref country code: BE

Payment date: 20230316

Year of fee payment: 9

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230426

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

Ref country code: ES

Payment date: 20230405

Year of fee payment: 9

Ref country code: CH

Payment date: 20230430

Year of fee payment: 9

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

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; INVALID AB INITIO

Effective date: 20150303