EP1697277B1 - Thermal pre-ignition agents - Google Patents
Thermal pre-ignition agents Download PDFInfo
- Publication number
- EP1697277B1 EP1697277B1 EP04820421A EP04820421A EP1697277B1 EP 1697277 B1 EP1697277 B1 EP 1697277B1 EP 04820421 A EP04820421 A EP 04820421A EP 04820421 A EP04820421 A EP 04820421A EP 1697277 B1 EP1697277 B1 EP 1697277B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitrate
- thermal pre
- particularly preferably
- thermal
- ignition agents
- 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.)
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- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 18
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- -1 nitrogen-containing compound Chemical class 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229920001220 nitrocellulos Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 4
- YXYNPIWENOTEHZ-UHFFFAOYSA-N 2-nitramidoguanidine Chemical compound NC(=N)NN[N+]([O-])=O YXYNPIWENOTEHZ-UHFFFAOYSA-N 0.000 claims description 4
- QJTIRVUEVSKJTK-UHFFFAOYSA-N 5-nitro-1,2-dihydro-1,2,4-triazol-3-one Chemical compound [O-][N+](=O)C1=NC(=O)NN1 QJTIRVUEVSKJTK-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 4
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 claims description 4
- FQQQSNAVVZSYMB-UHFFFAOYSA-N 1,1-diaminoguanidine Chemical compound NN(N)C(N)=N FQQQSNAVVZSYMB-UHFFFAOYSA-N 0.000 claims description 3
- BVGPZRCQJJMXBI-UHFFFAOYSA-N 1,2-diaminoguanidine;nitric acid Chemical compound O[N+]([O-])=O.NN\C(N)=N/N BVGPZRCQJJMXBI-UHFFFAOYSA-N 0.000 claims description 3
- BAKYASSDAXQKKY-UHFFFAOYSA-N 4-Hydroxy-3-methylbenzaldehyde Chemical compound CC1=CC(C=O)=CC=C1O BAKYASSDAXQKKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- 239000000028 HMX Substances 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- UAGLZAPCOXRKPH-UHFFFAOYSA-N nitric acid;1,2,3-triaminoguanidine Chemical compound O[N+]([O-])=O.NNC(NN)=NN UAGLZAPCOXRKPH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 150000003873 salicylate salts Chemical class 0.000 claims description 3
- 150000004760 silicates Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910000568 zirconium hydride Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical class CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 claims 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 1
- 229910010277 boron hydride Inorganic materials 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 43
- 238000004200 deflagration Methods 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 6
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 4
- DBERHVIZRVGDFO-UHFFFAOYSA-N Acetoxyacetone Chemical compound CC(=O)COC(C)=O DBERHVIZRVGDFO-UHFFFAOYSA-N 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- VEUADMFEHDOAMG-UHFFFAOYSA-N NC(NN)=N.[O-][N+](NC1=NN=NN1)=O Chemical compound NC(NN)=N.[O-][N+](NC1=NN=NN1)=O VEUADMFEHDOAMG-UHFFFAOYSA-N 0.000 description 3
- VGGYAUGSUUKNPW-UHFFFAOYSA-N azane N-(2H-tetrazol-5-yl)nitramide Chemical compound C1(=NNN=N1)N[N+](=O)[O-].N VGGYAUGSUUKNPW-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FRMYHJIXCLBUCK-UHFFFAOYSA-N 5-nitrotriazol-4-one Chemical compound [O-][N+](=O)C1=NN=NC1=O FRMYHJIXCLBUCK-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229950008501 aminoethyl nitrate Drugs 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C7/00—Non-electric detonators; Blasting caps; Primers
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C9/00—Chemical contact igniters; Chemical lighters
Definitions
- the present invention relates to pre-ignition agents which can be used, for example, as thermal fuses in gas generators for motor vehicle safety systems.
- Thermal pre-ignition agents are pyrotechnic substances or mixtures. They have, inter alia, the task to ignite the usually thermally very stable gas-generating mixtures of the gas generator in the event of a vehicle fire in a controlled manner.
- thermal thermal ignition agents are nitrocellulose, propellant powders derived therefrom or those disclosed in the patent application DE 197 30 873 A1 used mixtures based on nitrotriazolone and Guanidinnitraf. These mixtures show ignition temperatures of about 160 ° C and are insufficiently long-term stability in the case of nitrocellulose.
- EP-A-0 665 138 discloses a thermal preignition agent as a thermal fuse in gas generators containing sugar, a chlorate or perchlorate (eg KClO 3 , NaClO 3 or KClO 4 ) and a synthetic resin.
- a chlorate or perchlorate eg KClO 3 , NaClO 3 or KClO 4
- the object of the present invention was to provide pyrotechnic mixtures with ignition temperatures around 200 ° C. and sufficient long-term stability, which can be used as thermal premature ignition agents for gas generators in motor vehicle safety systems.
- the problem underlying the invention was solved by the use of 2- [bis (2,4,6-trinitrophenyl)] aminoethyl nitrate, abbreviated to Dipikrylaminoethylnitrat (DPN). This substance can be used in mixtures with other components.
- DPN can be prepared from 2,4-dinitrochlorobenzene and ethanolamine followed by nitration (Lit .: RV Clark, Ind. Eng. Chem., 25, 1385 (1933 )).
- the structural formula is as follows:
- the deflagration point of pure DPN is approx. 200 ° C.
- the deflagration point can be controlled in the range from 178.degree. C. to 208.degree. C. and the deflagration temperatures of the mixtures can be lower than those of the individual components.
- Those of the individual components For Teczündstoff deflagration temperatures below 200 ° C are particularly interesting.
- the mixtures according to the invention meet this requirement with excellent long-term stability.
- the production and processing takes place according to known and customary methods. These include, for example, kneading, extrusion, extrusion, tabletting or granulation.
- Table 1 shows the compositions of twelve different mixtures. The components were weighed in the stated weight ratios (percentages by weight (% by weight)) in plastic containers and homogenized for 30 minutes in a tumble mixer. Table 1: Examples mixture DPN in% by weight Nitroguanidine in wt.% 5-aminotetrazole in wt.% Guanidine nitrate in% by weight Potassium nitrate in wt.% Sodium nitrate in wt.% Potassium perchlorate in wt.% 1 50 50 2 50 5 50 4 20 30 50 5 20 30 50 6 20 30 50 7 20 30 50 8th 20 30 50 9 20 30 50 10 20 30 50 11 20 30 50 12 20 30 50
- Table 2 shows the explosion heats, friction and impact sensitivities of the blends.
- the measurement of the friction and impact sensitivities was carried out according to methods of the Federal Institute for Materials Research (BAM), while the measurement of the explosion heat was carried out with a calorimeter from EKA.
- Table 3 summarizes the deflagration points before and after thermal stress (400 h, 110 ° C) and the weight losses after 72 h and 400 h thermal stress at 110 ° C.
- the determination of the deflagration points was carried out by thermogravimetric analysis (Mettler) at a heating rate of 10 ° C per minute. The weight loss was measured analogously to the Holland test.
- Thermal Fruhzündstoff containing 10 to 90 wt.%, Preferably 25 to 75 wt.%, Particularly preferably 40 to 60 wt.% Dipikrylaminoethylnitrat and 10 to 90 wt.%, Preferably 25 to 75 wt.%, Particularly preferably 40 to 60 wt % of an oxidizing agent.
- Thermal preignition agents containing 10 to 90 wt.% Preferably 10 to 50 wt.%, Particularly preferably 10 to 30 wt.% Of dipicrylaminoethyl nitrate, 10 to 90 wt.%, Preferably 10 to 60 wt.%, Particularly preferably 20 to 40 wt .% Of a nitrogen-containing compound and 10 to 90 wt.%, Preferably 25 to 75 wt.%, Particularly preferably 40 to 60 wt.% Of an oxidizing agent.
- Thermal preignition agents containing, in addition to DPN, nitrogen-containing compounds, singly or in mixtures, such as nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole, such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and salts thereof, nitraminotetrazole and its salts such as ammonium nitraminotetrazole and aminoguanidinium nitraminotetrazole, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamide nitrate, diaminoguanidine azotetrazolate.
- nitrogen-containing compounds such as nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole, such as 5-aminotetrazole, ditetrazolylamine
- oxidizing agents in addition to DPN and the above-mentioned nitrogenous compounds, individually or in mixtures, oxidizing agents, individually or in mixtures, such as nitrates of alkali or alkaline earth metals or ammonium such as sodium nitrate or potassium nitrate, perchlorates of alkali or alkaline earth metals or of ammonium, peroxides of alkaline earth metals or of zinc.
- Thermal preignition agents which, in addition to DPN, the abovementioned nitrogenous compounds, individually or in mixtures and / or the abovementioned oxidizing agents, individually or in mixtures, reducing agents, individually or in mixtures, in proportions by weight of 1 to 80%, such as aluminum, Titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black.
- Thermal preignition agents which, in addition to DPN, the abovementioned nitrogen-containing compounds, individually or in mixtures, the abovementioned oxidizing agents, individually or in mixtures and / or the abovementioned reducing agents, individually or in mixtures, binders, individually or in mixtures, in parts by weight of 1 to 80%, such as cellulose and its derivatives, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and copolymers.
- Thermal preignition agents which, in addition to DPN, the abovementioned nitrogen-containing compounds, individually or in mixtures, the abovementioned oxidizing agents, individually or in mixtures, the abovementioned reducing agents, individually or in mixtures and / or the abovementioned binders, individually or in mixtures, energetic additives, individually or in mixtures, in proportions by weight of 10 to 80%, such as. Hexogen, octogen and nitrocellulose.
- Thermal preignition agents which, in addition to DPN, the abovementioned nitrogenous compounds, individually or in mixtures, the abovementioned oxidizing agents, individually or in mixtures, the above-mentioned reducing agents, individually or in Mixtures, the above-mentioned binders, individually or in mixtures and / or the above energetic additives, individually or in mixtures, Abbrandmoderatoren and processing aids, individually or in mixtures, in proportions by weight of 0.1 to 20%, such as ferrocene and derivatives , Acetonyl acetates, salicylates, silicates, silica gels, boron nitride.
Abstract
Description
Gegenstand der vorliegenden Erfindung sind Frühzündmittel, die beispielsweise als thermische Sicherungen in Gasgeneratoren für Kraftfahrzeugsicherheitssysteme eingesetzt werden können.The present invention relates to pre-ignition agents which can be used, for example, as thermal fuses in gas generators for motor vehicle safety systems.
Thermische Frühzündmittel sind pyrotechnische Substanzen bzw. Mischungen. Sie haben unter anderem die Aufgabe, die in der Regel thermisch sehr stabilen gaserzeugenden Mischungen des Gasgenerators im Falle eines Fahrzeugbrandes kontrolliert anzuzünden.Thermal pre-ignition agents are pyrotechnic substances or mixtures. They have, inter alia, the task to ignite the usually thermally very stable gas-generating mixtures of the gas generator in the event of a vehicle fire in a controlled manner.
Als thermische Frühzündmittel werden beispielsweise Nitrocellulose, daraus abgeleitete Treibladungspulver oder die in der Patentanmeldung
Aufgabe der vorliegenden Erfindung war die Bereitstellung von pyrotechnischen Mischungen mit Entzündungstemperaturen um 200°C und ausreichender Langzeitstabilität, die als thermische Frühzündmittel für Gasgeneratoren in Kraftfahrzeugsicherheitssystemen eingesetzt werden können. Gelöst wurde die der Erfindung zu Grunde liegende Aufgabe durch den Einsatz von 2-[Bis-(2,4,6-trinitrophenyl)] aminoethylnitrat, kurz als Dipikrylaminoethylnitrat (DPN) bezeichnet. Diese Substanz kann in Mischungen mit weiteren Komponenten verwendet werden. DPN kann aus 2,4-Dinitrochlorbenzol und Ethanolamin mit anschließender Nitrierung hergestellt werden (Lit.: 
Der Verpuffungspunkt von reinem DPN liegt bei ca. 200°C. Überraschenderweise wurde gefunden, dass sich bei Mischungen von DPN mit ausgewählten Komponenten als Zusatzstoffe der Verpuffungspunkt im Bereich von 178°C bis 208°C steuern lässt und die Verpuffungstemperaturen der Mischungen tiefer liegen können als die der Einzelkomponenten. Für Frühzündmittel sind Verpuffungstemperaturen unter 200°C besonders interessant. Die erfindungsgemäßen Mischungen erfüllen diese Forderung bei ausgezeichneter Langzeitstabilität.The deflagration point of pure DPN is approx. 200 ° C. Surprisingly, it has been found that in the case of mixtures of DPN with selected components as additives, the deflagration point can be controlled in the range from 178.degree. C. to 208.degree. C. and the deflagration temperatures of the mixtures can be lower than those of the individual components. For Frühzündmittel deflagration temperatures below 200 ° C are particularly interesting. The mixtures according to the invention meet this requirement with excellent long-term stability.
Als Zusatzstoffe können verwendet werden:
- 1. Stickstoffhaltige Verbindungen (einzeln oder in Mischungen)
Nitroguanidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols wie 5-Aminotetrazol, Ditetrazolylamin, Ditetrazol und deren Salze, Nitraminotetrazol und seine Salze wie Ammonium-Nitraminotetrazol und Aminoguanidinium-Nitraminotetrazol, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-Azotetrazolat. - 2. Oxidationsmittel (einzeln oder in Mischungen)
Nitrate der Alkali- oder Erdalkalimetalle oder des Ammoniums wie Natriumnitrat oder Kaliumnitrat, Perchlorate der Alkali- oder Erdalkalimetalle oder des Ammoniums, Peroxide der Erdalkalimetalle oder des Zinks. - 3. Reduktionsmittel (einzeln oder in Mischungen)
Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß. - 4. Bindemittel (einzeln oder in Mischungen)
Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymere. - 5. Energiereiche Zuschläge (einzeln oder in Mischungen)
Hexogen, Oktogen und Nitrocellulose. - 6. Abbrandmoderatoren und Verarbeitungshilfen (einzeln oder in Mischungen) Ferrocen und Derivate , Acetonylacetate, Salicylate, Silikate, Kieselgele, Bornitrid.
- 1. Nitrogen-containing compounds (individually or in mixtures)
Nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and salts thereof, nitraminotetrazole and its salts such as ammonium nitraminotetrazole and aminoguanidinium nitraminotetrazole, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamide nitrate, diaminoguanidine azotetrazolate. - 2. Oxidizing agents (individually or in mixtures)
Nitrates of the alkali or alkaline earth metals or of ammonium, such as sodium nitrate or potassium nitrate, perchlorates of the alkali or alkaline earth metals or of ammonium, peroxides of the alkaline earth metals or of zinc. - 3. Reducing agent (individually or in mixtures)
Aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black. - 4. Binders (individually or in mixtures)
Cellulose and its derivatives, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and copolymers. - 5. High-energy supplements (individually or in mixtures)
Hexogen, octogen and nitrocellulose. - 6. Abrasion moderators and processing aids (individually or in mixtures) ferrocene and derivatives, acetonyl acetates, salicylates, silicates, silica gels, boron nitride.
Die Herstellung und Verarbeitung findet nach an sich bekannten und üblichen Verfahren statt. Hierzu zählen beispielsweise Kneten, Extrudieren, Strangpressen, Tablettieren oder Granulieren.The production and processing takes place according to known and customary methods. These include, for example, kneading, extrusion, extrusion, tabletting or granulation.
Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne sie einzuschränken.The following examples are intended to illustrate the invention without limiting it.
In Tabelle 1 sind die Zusammensetzungen von zwölf verschiedenen Mischungen dargestellt. Die Komponenten wurden in den angegebenen Gewichtsverhältnissen (Angaben in Gewichtsprozent (Gew.%)) in Plastikbehälter eingewogen und 30 Minuten im Taumelmischer homogenisiert.
In Tabelle 2 sind die Explosionswärmen, Reib- und Schlagempfindlichkeiten der Mischungen dargestellt. Die Messung der Reib- und Schlagempfindlichkeiten erfolgte nach Methoden der Bundesanstalt für Materialforschung (BAM), während die Messung der Explosionswärmen mit einem Kalorimeter der Fa. EKA durchgeführt wurden.
In Tabelle 3 sind die Verpuffungspunkte vor und nach thermischer Belastung (400 h, 110°C) und die Gewichtsverluste nach 72 h und 400 h thermischer Belastung bei 110°C zusammengefasst. Die Bestimmung der Verpuffungspunkte erfolgte mit der Thermogravimetrie-Analyse (Fa. Mettler) bei einer Aufheizrate von 10°C pro Minute. Die Messung des Gewichtsverlustes erfolgte analog dem Holland Test.Table 3 summarizes the deflagration points before and after thermal stress (400 h, 110 ° C) and the weight losses after 72 h and 400 h thermal stress at 110 ° C. The determination of the deflagration points was carried out by thermogravimetric analysis (Mettler) at a heating rate of 10 ° C per minute. The weight loss was measured analogously to the Holland test.
Man erkennt nach 400 h nur geringe Gewichtsverluste von 0,2 bis 0,5 Gew.% und keine signfikante Änderung der Verpuffungstemperatur nach thermischer Belastung.
Die Beispiele zeigen, dass die erfindungsgemäß definierten Mischungen Verpuffungstemperaturen im Bereich von 178 bis 208°C aufweisen und gemäß den Forderungen der Automobilindustrie als stabil anzusehen sind.The examples show that the mixtures defined according to the invention have deflagration temperatures in the range from 178 to 208 ° C. and are to be regarded as stable according to the requirements of the automotive industry.
Gegenstand der vorliegenden Erfindung sind im Einzelnen:The subject of the present invention are in detail:
Thermische Fruhzündmittel, die 10 bis 90 Gew.%, vorzugsweise 25 bis 75 Gew.%, besonders bevorzugt 40 bis 60 Gew.% Dipikrylaminoethylnitrat und 10 bis 90 Gew.%, vorzugsweise 25 bis 75 Gew.%, besonders bevorzugt 40 bis 60 Gew.% eines Oxidationsmittels enthalten.Thermal Fruhzündmittel containing 10 to 90 wt.%, Preferably 25 to 75 wt.%, Particularly preferably 40 to 60 wt.% Dipikrylaminoethylnitrat and 10 to 90 wt.%, Preferably 25 to 75 wt.%, Particularly preferably 40 to 60 wt % of an oxidizing agent.
Thermische Frühzundmittel, die 10 bis 90 Gew.%, vorzugsweise 10 bis 50 Gew.%, besonders bevorzugt 10 bis 30 Gew.% Dipikrylaminoethylnitrat, 10 bis 90 Gew.%, vorzugsweise 10 bis 60 Gew.%, besonders bevorzugt 20 bis 40 Gew.% einer stickstoffhaltigen Verbindung und 10 bis 90 Gew.%, vorzugsweise 25 bis 75 Gew.%, besonders bevorzugt 40 bis 60 Gew.% eines Oxidationsmittels enthalten.Thermal preignition agents containing 10 to 90 wt.%, Preferably 10 to 50 wt.%, Particularly preferably 10 to 30 wt.% Of dipicrylaminoethyl nitrate, 10 to 90 wt.%, Preferably 10 to 60 wt.%, Particularly preferably 20 to 40 wt .% Of a nitrogen-containing compound and 10 to 90 wt.%, Preferably 25 to 75 wt.%, Particularly preferably 40 to 60 wt.% Of an oxidizing agent.
Thermische Frühzündmittel, die neben DPN stickstoffhaltige Verbindungen, einzeln oder in Mischungen, enthalten, wie beispielsweise Nitroguanidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols wie 5-Aminotetrazol, Ditetrazolylamin, Ditetrazol und deren Salze, Nitraminotetrazol und seine Salze wie Ammonium-Nitraminotetrazol und Aminoguanidinium-Nitraminotetrazol, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-Azotetrazolat.Thermal preignition agents containing, in addition to DPN, nitrogen-containing compounds, singly or in mixtures, such as nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole, such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and salts thereof, nitraminotetrazole and its salts such as ammonium nitraminotetrazole and aminoguanidinium nitraminotetrazole, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamide nitrate, diaminoguanidine azotetrazolate.
Thermische Frühzündmittel, die neben DPN und den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, Oxidationsmittel, einzeln oder in Mischungen, enthalten, wie beispielsweise Nitrate der Alkali- oder Erdalkalimetalle oder des Ammoniums wie Natriumnitrat oder Kaliumnitrat, Perchlorate der Alkali- oder Erdalkalimetalle oder des Ammoniums, Peroxide der Erdalkalimetalle oder des Zinks.Thermal Frühzündmittel, in addition to DPN and the above-mentioned nitrogenous compounds, individually or in mixtures, oxidizing agents, individually or in mixtures, such as nitrates of alkali or alkaline earth metals or ammonium such as sodium nitrate or potassium nitrate, perchlorates of alkali or alkaline earth metals or of ammonium, peroxides of alkaline earth metals or of zinc.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen und/oder den oben genannten Oxidationsmitteln, einzeln oder in Mischungen, Reduktionsmittel, einzeln oder in Mischungen, in Gewichtsanteilen von 1 bis 80 % enthalten, wie beispielsweise Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß.Thermal preignition agents which, in addition to DPN, the abovementioned nitrogenous compounds, individually or in mixtures and / or the abovementioned oxidizing agents, individually or in mixtures, reducing agents, individually or in mixtures, in proportions by weight of 1 to 80%, such as aluminum, Titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, den oben genannten Oxidationsmitteln, einzeln oder in Mischungen und/oder den oben genannten Reduktionsmitteln, einzeln oder in Mischungen, Bindemittel, einzeln oder in Mischungen, in Gewichtsanteilen von 1 bis 80 % enthalten, wie beispielsweise Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymere.Thermal preignition agents which, in addition to DPN, the abovementioned nitrogen-containing compounds, individually or in mixtures, the abovementioned oxidizing agents, individually or in mixtures and / or the abovementioned reducing agents, individually or in mixtures, binders, individually or in mixtures, in parts by weight of 1 to 80%, such as cellulose and its derivatives, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and copolymers.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, den oben genannten Oxidationsmitteln, einzeln oder in Mischungen, den oben genannten Reduktionsmitteln, einzeln oder in Mischungen und/oder den oben genannten Bindemitteln, einzeln oder in Mischungen, energetische Zusätze, einzeln oder in Mischungen, in Gewichtsanteilen von 10 bis 80 % enthalten, wie beispielsweise. Hexogen, Oktogen und Nitrocellulose.Thermal preignition agents which, in addition to DPN, the abovementioned nitrogen-containing compounds, individually or in mixtures, the abovementioned oxidizing agents, individually or in mixtures, the abovementioned reducing agents, individually or in mixtures and / or the abovementioned binders, individually or in mixtures, energetic additives, individually or in mixtures, in proportions by weight of 10 to 80%, such as. Hexogen, octogen and nitrocellulose.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, den oben genannten Oxidationsmitteln, einzeln oder in Mischungen, den oben genannten Reduktionsmitteln, einzeln oder in Mischungen, den oben genannten Bindemitteln, einzeln oder in Mischungen und/oder den oben genannten energetischen Zusätzen, einzeln oder in Mischungen, Abbrandmoderatoren und Verarbeitungshilfen, einzeln oder in Mischungen, in Gewichtsanteilen von 0,1 bis 20 % enthalten, wie beispielsweise Ferrocen und Derivate, Acetonylacetate, Salicylate, Silikate, Kieselgele, Bornitrid.Thermal preignition agents which, in addition to DPN, the abovementioned nitrogenous compounds, individually or in mixtures, the abovementioned oxidizing agents, individually or in mixtures, the above-mentioned reducing agents, individually or in Mixtures, the above-mentioned binders, individually or in mixtures and / or the above energetic additives, individually or in mixtures, Abbrandmoderatoren and processing aids, individually or in mixtures, in proportions by weight of 0.1 to 20%, such as ferrocene and derivatives , Acetonyl acetates, salicylates, silicates, silica gels, boron nitride.
Claims (9)
- Thermal pre-ignition agents containing from 10 to 90 wt.%, preferably from 25 to 75 wt.%, particularly preferably from 40 to 60 wt.%, dipicrylaminoethyl nitrate and from 10 to 90 wt.%, preferably from 25 to 75 wt.%, particularly preferably from 40 to 60 wt.%, of an oxidising agent.
- Thermal pre-ignition agents containing from 10 to 90 wt.%, preferably from 10 to 50 wt.%, particularly preferably from 10 to 30 wt.%, dipicrylaminoethyl nitrate, from 10 to 90 wt.%, preferably from 10 to 60 wt.%, particularly preferably from 20 to 40 wt.%, of a nitrogen-containing compound and from 10 to 90 wt.%, preferably from 25 to 75 wt.%, particularly preferably from 40 to 60 wt.%, of an oxidising agent.
- Thermal pre-ignition agents according to claim 1 or 2, characterised in that the oxidising agent is selected from one or more of the nitrates of the alkali and/or alkaline earth metals and/or of ammonium, of the perchlorates of the alkali and/or alkaline earth metals and/or of ammonium, of the peroxides of the alkaline earth metals and/or of zinc.
- Thermal pre-ignition agents according to claim 2 or 3, characterised in that the nitrogen-containing compound is selected from one or more of nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and/or salts thereof, nitraminotetrazole and/or its salts, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate.
- Thermal pre-ignition agents according to one or more of claims 1 to 4, characterised in that they contain from 1 to 80 wt.%, preferably from 1 to 40 wt.%, particularly preferably from 1 to 15 wt.%, of a reducing agent, preferably selected from one or more of aluminium, titanium, titanium hydride, boron, boron hydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black.
- Thermal pre-ignition agents according to one or more of claims 1 to 5, characterised in that they contain from 1 to 80 wt.%, preferably from 1 to 40 wt.%, particularly preferably from 1 to 20 wt.%, of a binder, preferably selected from one or more of cellulose and derivatives thereof, polyvinylbutyrals, polynitropolyphenylene, polynitrophenyl ether, Plexigum, polyvinyl acetate and copolymers.
- Thermal pre-ignition agents according to one or more of claims 1 to 6, characterised in that they contain from 10 to 80 wt.%, preferably from 10 to 50 wt.%, particularly preferably from 10 to 30 wt.%, high-energy additives, preferably selected from one or more of hexogen, octogen and nitrocellulose.
- Thermal pre-ignition agents according to one or more of claims 1 to 7, characterised in that they contain from 0.1 to 20 wt.%, preferably from 0.1 to 10 wt.%, combustion moderators and processing aids, preferably selected from one or more of ferrocene and derivatives thereof, acetonylacetates, salicylates, silicates, silica gels and boron nitride.
- Use of a thermal pre-ignition agent according to one or more of claims 1 to 8 as a thermal fuse in gas generators for motor vehicle safety systems.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10359536 | 2003-12-17 | ||
| DE102004045900 | 2004-09-22 | ||
| PCT/EP2004/013899 WO2005058775A1 (en) | 2003-12-17 | 2004-12-07 | Thermal pre-ignition agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1697277A1 EP1697277A1 (en) | 2006-09-06 |
| EP1697277B1 true EP1697277B1 (en) | 2009-03-25 |
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ID=34701998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04820421A Not-in-force EP1697277B1 (en) | 2003-12-17 | 2004-12-07 | Thermal pre-ignition agents |
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| Country | Link |
|---|---|
| US (1) | US8016959B2 (en) |
| EP (1) | EP1697277B1 (en) |
| JP (1) | JP5044219B2 (en) |
| AT (1) | ATE426580T1 (en) |
| AU (1) | AU2004299219B2 (en) |
| CA (1) | CA2549766C (en) |
| DE (1) | DE502004009241D1 (en) |
| IL (1) | IL176299A (en) |
| NO (1) | NO337562B1 (en) |
| WO (1) | WO2005058775A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017118416A1 (en) | 2017-08-11 | 2019-02-14 | Ruag Ammotec Gmbh | Pyrotechnic separator, system for electrically charging an electric power cell, mobile device and charger |
| RU2769553C1 (en) * | 2021-07-29 | 2022-04-04 | Умар Хамидович Булатов | Heat-resistant shaped charge |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1935495A (en) * | 1931-01-22 | 1933-11-14 | Atlas Powder Co | Slow match composition |
| US3320882A (en) * | 1964-09-01 | 1967-05-23 | Du Pont | High velocity ignition-propagating cord |
| US3734476A (en) * | 1971-09-13 | 1973-05-22 | United Aircraft Corp | Cutting torch |
| US4379007A (en) * | 1981-03-16 | 1983-04-05 | The United States Of America As Represented By The Secretary Of The Army | Catalysts for nitramine propellants |
| JPH07232613A (en) * | 1993-12-28 | 1995-09-05 | Nippon Kayaku Co Ltd | Gas generator for air bag and squib |
-
2004
- 2004-12-07 EP EP04820421A patent/EP1697277B1/en not_active Not-in-force
- 2004-12-07 DE DE502004009241T patent/DE502004009241D1/en active Active
- 2004-12-07 AT AT04820421T patent/ATE426580T1/en active
- 2004-12-07 CA CA2549766A patent/CA2549766C/en not_active Expired - Fee Related
- 2004-12-07 JP JP2006544279A patent/JP5044219B2/en not_active Expired - Fee Related
- 2004-12-07 WO PCT/EP2004/013899 patent/WO2005058775A1/en active Application Filing
- 2004-12-07 US US10/583,510 patent/US8016959B2/en not_active Expired - Fee Related
- 2004-12-07 AU AU2004299219A patent/AU2004299219B2/en not_active Ceased
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- 2006-06-14 IL IL176299A patent/IL176299A/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| NO337562B1 (en) | 2016-05-09 |
| CA2549766C (en) | 2011-08-23 |
| AU2004299219B2 (en) | 2012-01-12 |
| NO20063259L (en) | 2006-09-14 |
| ATE426580T1 (en) | 2009-04-15 |
| WO2005058775A1 (en) | 2005-06-30 |
| JP2007534581A (en) | 2007-11-29 |
| AU2004299219A1 (en) | 2005-06-30 |
| IL176299A0 (en) | 2006-10-05 |
| IL176299A (en) | 2011-03-31 |
| JP5044219B2 (en) | 2012-10-10 |
| CA2549766A1 (en) | 2005-06-30 |
| EP1697277A1 (en) | 2006-09-06 |
| US8016959B2 (en) | 2011-09-13 |
| US20080043385A1 (en) | 2008-02-21 |
| DE502004009241D1 (en) | 2009-05-07 |
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