CN1210234C - 含有三嗪衍生物的产气组合物 - Google Patents
含有三嗪衍生物的产气组合物 Download PDFInfo
- Publication number
- CN1210234C CN1210234C CNB018045464A CN01804546A CN1210234C CN 1210234 C CN1210234 C CN 1210234C CN B018045464 A CNB018045464 A CN B018045464A CN 01804546 A CN01804546 A CN 01804546A CN 1210234 C CN1210234 C CN 1210234C
- Authority
- CN
- China
- Prior art keywords
- weight
- composition
- melamine
- oxide
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims abstract description 81
- 229910002010 basic metal nitrate Inorganic materials 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 67
- 229920000877 Melamine resin Polymers 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 32
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 claims description 18
- -1 melamine compound Chemical class 0.000 claims description 18
- 229920002907 Guar gum Polymers 0.000 claims description 15
- 239000000665 guar gum Substances 0.000 claims description 15
- 229960002154 guar gum Drugs 0.000 claims description 15
- 235000010417 guar gum Nutrition 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 2
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 2
- 229920000800 acrylic rubber Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- CSGNMMLYYZTWBB-UHFFFAOYSA-N nitric acid;1,3,5-triazine-2,4,6-triamine Chemical compound O[N+]([O-])=O.NC1=NC(N)=NC(N)=N1 CSGNMMLYYZTWBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 claims description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 2
- ZFPPQTYHQHJOOI-UHFFFAOYSA-N perchloric acid;1,3,5-triazine-2,4,6-triamine Chemical compound [O-]Cl(=O)(=O)=O.NC1=NC(N)=[NH+]C(N)=N1 ZFPPQTYHQHJOOI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims 1
- BJCMJNYBUSSWPP-UHFFFAOYSA-N n-(4,6-diamino-1,3,5-triazin-2-yl)nitramide Chemical compound NC1=NC(N)=NC(N[N+]([O-])=O)=N1 BJCMJNYBUSSWPP-UHFFFAOYSA-N 0.000 claims 1
- 150000004965 peroxy acids Chemical class 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 24
- 239000011230 binding agent Substances 0.000 abstract 2
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 150000003918 triazines Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 125000003831 tetrazolyl group Chemical group 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- HMJLQBHYCJMPMK-UHFFFAOYSA-N hydrazine;triazine Chemical class NN.C1=CN=NN=C1 HMJLQBHYCJMPMK-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 150000003921 pyrrolotriazines Chemical class 0.000 description 4
- 230000004927 fusion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 150000004972 metal peroxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- 150000000182 1,3,5-triazines Chemical class 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 150000001337 aliphatic alkines Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 description 1
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- HOWFTCIROIVKLW-UHFFFAOYSA-L strontium;dinitrite Chemical compound [Sr+2].[O-]N=O.[O-]N=O HOWFTCIROIVKLW-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- 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)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
- B60R21/263—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using a variable source, e.g. plural stage or controlled output
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
- B60R21/264—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic
- B60R21/2644—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic using only solid reacting substances, e.g. pellets, powder
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Air Bags (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Abstract
公开了一种包括(a)三嗪衍生物、(b)碱式金属硝酸盐、和非必要地(c)粘合剂和/或(d)添加剂的产气组合物。该产气组合物降低了毒性、并提高燃烧速率和降低燃烧温度。
Description
发明领域
本发明涉及适宜于汽车等的气囊束缚系统的产气组合物、其模制品和用其的用于气囊的充气机。
相关技术
关于用作汽车乘客保护系统的气囊的产气剂,至今常常使用用叠氮化钠的组合物。然而,认为叠氮化钠对人体的毒性[LD50(口服-小鼠)=27mg/kg]或处理叠氮化钠中的危害性是一个严重的问题。因此,已开发了含有各种含氮有机化合物的产气组合物作为安全的非叠氮化物基的产气组合物。
例如,US-A 4909549公开了一种包括含氢四唑或三唑化合物和含氧氧化剂的组合物。US-A 4370181公开了包括无氢双四唑金属盐和无氧氧化剂的产气组合物。US-A4369079公开了一种包括无氢双四唑金属盐、碱金属硝酸盐、碱金属亚硝酸盐、碱土金属硝酸盐、碱土金属亚硝酸盐、或其混合物的产气组合物。US-A 5542999公开了一种包括如GZT、TAGN、NG(硝基胍)、NTO等的燃料、碱式硝酸盐、还原有毒气体的催化剂和冷却剂的产气剂。JP-A 10-72273公开了一种包括双四唑盐、双四唑铵盐或氨基四唑和硝酸铵的产气剂。
然而,非叠化物基的产气组合物在燃烧温度、燃烧速率、相转移、产生的一氧化碳和氧化氮的量、气体输出等方面是有问题的。例如,US-A4369079的产气组合物具有高的燃烧温度,并在实际使用时需要大量的冷却剂。US-A 5542999的组合物具有低的燃烧速率,并在短时间内不能完全燃烧。在JP-A10-72273的产气剂中,在使用温度中由于硝酸铵的相转移,模制件的形状发生变化,其损坏了产气剂的模制件,结果,不能得到稳定的燃烧。另外,在这些基于非叠氮化物基的产气剂的相关技术中,四唑、硝基胍和TAGN被用作产气剂的燃料。然而,这些化合物全是有害的材料,当处理它们时出于安全考虑必须特别小心。
发明公开
因此,本发明的一个目的是提供燃烧温度低、燃烧速率高、产生的一氧化碳和氧化氮的量低、燃烧稳定性好和处理时安全性高的产气组合物、其模制件和用其的气囊用充气机。
本发明提供了一种产气组合物,包括(a)三嗪衍生物和(b)氧化剂。
另外,本发明提供一种由该产气组合物制备的呈单孔柱形、孔状(多孔)柱形或粒状的模制件。
本发明还提供了一种使用该产气组合物和模制件的气囊用充气机。
本发明的产气组合物和模制件由于低毒性和几乎无害而容易处理。另外,燃烧速率高,燃烧温度低,在燃烧时产生的一氧化碳和氧化氮的量得以降低。
本发明的实施方式
用于本发明的作为组分(a)的三嗪衍生物是优选的,这是由于其毒性低,且在与组分(b)组合使用时,燃烧温度低且提高了燃烧速率。
关于三嗪衍生物,可提到选自三嗪(1,2,3-三嗪、1,2,4-三嗪或1,3,5-三嗪)、蜜胺、三肼基三嗪、三羟甲基蜜胺、烷基化羟甲基蜜胺、三聚氰酸二酰胺、三聚氰酸一酰胺、ammelande、氰尿酸、氰尿酸衍生物如氰尿酸酯、蜜白胺、蜜勒胺、硝酸蜜胺、高氯酸蜜胺、和蜜胺的硝基化合物如二硝基三聚氰酸二酰胺中的至少一种。
其中,优选蜜胺和三肼基三嗪(THT),这是因为LD50(口服-小鼠)=3.161mg/kg,燃烧稳定性高,在处理性安全性好且成本低。
关于用于本发明的作为组分(b)的氧化剂,可提到选自含氧酸盐、金属氧化物、金属双氧化物、金属过氧化物和碱式金属硝酸盐中的至少一种。其中,优选碱式金属硝酸盐,特别优选碱式硝酸铜。
含氧酸盐包括含选自铵、碱金属和碱土金属的阳离子和选自硝酸、亚硝酸、氯酸、和高氯酸的无氢阴离子的盐。
这种含氧酸盐的例子包括硝酸的铵盐、碱金属盐和碱土金属盐,如硝酸铵、硝酸钠、硝酸钾、硝酸镁和硝酸锶;亚硝酸的铵盐、碱金属盐和碱土金属盐,如亚硝酸铵、亚硝酸钠、亚硝酸钾、亚硝酸镁和亚硝酸锶;氯酸的铵盐、碱金属盐和碱土金属盐,如氯酸铵、氯酸钠、氯酸钾、氯酸镁和氯酸钡;高氯酸的铵盐、碱金属盐和碱土金属盐,如高氯酸铵、高氯酸钠、高氯酸钾、高氯酸镁和高氯酸钡。
金属氧化物、金属过氧化物和金属双氧化物包括铜、钴、铁、镁、镍、锌、钼和铋的氧化物、过氧化物和双氧化物。
金属氧化物、过氧化物和金属双氧化物的例子可包括CuO,Cu2O,Co2O3,CoO,Co3O4,Fe2O3,FeO,Fe3O4,MnO2,Mn3O4,NiO,ZnO,MoO3,CoMoO4,Bi2MoO6,和Bi2O3。
碱式金属硝酸盐包括由下式表示的一些化合物。另外一些化合物包括其水合物。在该式中,M表示金属、x’表示金属的数目,y和y`表示NO3离子的数,z`表示OH离子的数,n表示M(OH)z部分与M(NO3)y部分之比。
M(NO3)y.nM(OH)z或Mx`(NO3)y`(OH)z`
对应于该式的化合物的例子包括含作为金属M的铜、钴、锌、锰、铁、钼、铋、铈的化合物,如Cu2(NO3)(OH)3、Cu3(NO3)(OH)5.2H2O、Co2(NO3)(OH)3、Zn2(NO3)(OH)3、Mn(NO3)(OH)2、Fe4(NO3)(OH)11.2H2O、Bi(NO3)(OH)2和Ce(NO3)(OH).3H2O。
关于碱式金属硝酸盐,提到选自碱式硝酸铜(BCN)、碱式硝酸钴、碱式硝酸锌、碱式硝酸锰、碱式硝酸铁、碱式硝酸钼、碱式硝酸铋和碱式硝酸铈的至少一种。其中,优选碱式硝酸铜。
相比于作为氧化剂的硝酸铵,碱式硝酸铜的热稳定性优良,这是因为在使用温度范围内没有出现相转移且熔点高。另外,由于碱式硝酸铜起作降低产气剂的燃烧温度的作用,产生的二氧化氮的量可以降低。
当本发明的产气组合物包括组分(a)和(b)时,组分(a)的量优选为5-60%重量,更优选为5-50%重量,进一步优选为10-30%重量,组分(b)的量优选为40-95%重量,更优选为50-95%重量,进一步优选为70-90%重量。
包括组分(a)和(b)的组合物的优选例子为包括(a)蜜胺和(b)碱式硝酸铜的组合物。在这种情形下,(a)蜜胺的量为15-45%重量,优选为15-25%重量,(b)碱式硝酸铜的量为55-85%重量,优选为75-85%重量。
包括组分(a)和(b)的组合物的另一优选例子为包括(a)三肼基三嗪和(b)碱式硝酸铜的组合物。在这种情形下,(a)三肼基三嗪的量为15-45%重量,优选为15-25%重量,(b)碱式硝酸铜的量为55-85%重量,优选为75-85%重量。
本发明的产气组合物还可含有粘合剂作为组分(c)来提高模制件的强度。
关于粘合剂,可提到选自下列的至少一种:羧甲基纤维素(CMC)、羧甲基纤维素钠盐(CMCNa)、羧甲基纤维素的钾盐、羧甲基纤维素的铵盐、乙酸纤维素、乙酸丁酸纤维素(CAB)、甲基纤维素(MC)、乙基纤维素(EC)、羟乙基纤维素(HEC)、乙基羟乙基纤维素(EHEC)、羟丙基纤维素(HPC)、羧甲基乙基纤维素(CMEC)、细结晶纤维素、聚丙烯酰胺、聚丙烯酰胺的胺产品、聚丙烯酰肼、丙烯酸酰胺和丙烯酸的金属盐的共聚物、聚丙烯酸酰胺和聚丙烯酸酯的共聚物、聚乙烯醇、丙烯酸酯橡胶、瓜尔胶、淀粉和硅氧烷。其中,考虑到粘性、成本和点燃性,优选羧甲基纤维素钠盐(CMCNa)和瓜尔胶。
本发明的产气组合物还可含有添加剂作为组分(d)来减少由于降低燃烧温度而燃烧后产生的有毒的氧化氮和一氧化碳的量。
关于添加剂,可提到选自下列的至少一种:金属氧化物如氧化铜、氧化铁、氧化钴、氧化锰、氧化钼、氧化镍、氧化铋、氧化硅和氧化铝;金属氢氧化物如氢氧化铝、氢氧化钴和氢氧化铁;金属碳酸盐或碱式金属碳酸盐如碳酸钴、碳酸钙、碱式碳酸锌和碱式碳酸铜;金属氧化物或氢氧化物的复合物如日本酸性粘土、高岭土、滑石、膨润土、硅藻土和水滑石(hydrotalcite);金属酸盐如硅酸钠、云母、钼酸盐、钼酸钴和钼酸铵;硅氧烷、二硫化钼、硬脂酸钙、氮化硅和碳化硅。其中优选氢氧化铝和氧化钴。
可使用组合(c)的粘合剂和组分(d)的添加剂的一种或两种。
当本发明的产气组合物包括组分(a)、(b)和(c)和/或(d)时,组分(a)的量优选为5-60%重量,更优选为10-25%重量,组分(b)的量优选为40-95%重量,更优选为40-85%重量,还优选为50-80%重量,组分(c)的量优选为0.1-15%重量,更优选为1-10%重量,组分(d)的量优选为0.1-20%重量,更优选为3-15%重量。
包括组分(a)、(b)和(c)的组合物的一个优选例子为包括(a)蜜胺、(b)碱式硝酸铜、和(c)羧甲基纤维素钠的组合物。在这种情形下,优选(a)蜜胺的量为15-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)羧甲基纤维素钠的量为0.1-10%重量。
包括组分(a)、(b)和(c)的组合物的另一个优选例子为包括(a)蜜胺、(b)碱式硝酸铜、和(c)瓜尔胶的组合物。在这种情形下,优选(a)蜜胺的量为15-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)瓜尔胶的量为0.1-10%重量。
包括组分(a)、(b)和(c)的组合物的另一个优选例子为包括(a)三肼三嗪、(b)碱式硝酸铜、和(c)瓜尔胶的组合物。在这种情形下,优选(a)三肼三嗪的量为15-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)瓜尔胶的量为0.1-10%重量。
包括组分(a)、(b)、(c)及(d)的组合物的一个优选例子为包括(a)蜜胺、(b)碱式硝酸铜、(c)羧甲基纤维素钠、和(d)氢氧化铝的组合物。在这种情形下,优选(a)蜜胺的量为10-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)羧甲基纤维素钠的量为0.1-10%重量,(d)氢氧化铝的量为1-15%重量。
包括组分(a)、(b)、(c)及(d)的组合物的另一个优选例子为包括(a)蜜胺、(b)碱式硝酸铜、(c)羧甲基纤维素钠、和(d)氧化钴的组合物。在这种情形下,优选(a)蜜胺的量为1 0-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)羧甲基纤维素钠的量为0.1-10%重量,(d)氧化钴的量为1-10%重量。
包括组分(a)、(b)、(c)及(d)的组合物的一个优选例子为包括(a)蜜胺、(b)碱式硝酸铜、(c)瓜尔胶、和(d)氢氧化铝的组合物。在这种情形下,优选(a)蜜胺的量为10-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)瓜尔胶的量为0.1-10%重量,(d)氢氧化铝的量为1-10%重量。
包括组分(a)、(b)、(c)及(d)的组合物的一个优选例子为包括(a)三肼三嗪、(b)碱式硝酸铜、(c)瓜尔胶、和(d)氢氧化铝的组合物。在这种情形下,优选(a)三肼三嗪的量为10-25%重量,(b)碱式硝酸铜的量为60-80%重量,(c)瓜尔胶的量为0.1-10%重量,(d)氢氧化铝的量为1-10%重量。
本发明的产气组合物可模制成所需的形状,并模制成呈单孔柱形、孔状(多孔)柱形或粒状的模制件。这些模制件可由把产气组合物与水或有机溶剂混合,并把该混合物挤塑来制备(模制件呈单孔状),或用造粒机挤塑模制来制备(模制件呈粒状)。
在本发明中得到的产气组合物或模制件可用于如驾驶员的气囊的充气机、乘客的气囊的充气机、和可充气垫的充气机、膝支持器的充气机、可充气座位带的充气机、各种车辆用于保护的带状系统和气体发生器。
另外,使用本发明所得的产气组合物或其模制件的充气机可为烟火型的,其中仅由产气剂来提供气体,或为混合型的,其中从压缩空气如氩等和产气剂两者来提供气体。
另外,本发明的产气组合物或其模制件也可用作称为促进剂(或传爆药)的点火剂,用于把雷管的能量传递到产气剂中。
实施例
本发明通过下面实施例和比较例来具体描述。然而,本发明并不局限于这些实施例。在表中,BCN表示碱式硝酸铜,CMCNa表示羧甲基纤维素钠,Gum表示瓜尔胶,BHTK表示双四唑钾,THT表示三肼三嗪。
实施例1-18和比较例1和2
制备每种具有表1所示的配方的产气组合物。根椐理论计算的这些组合物的燃烧温度、产气量(单位“mol/100”表示每100g组分物产生的气体的摩尔数)和产生的CO和NO的量示于表1中。
表1
配方(重量%) | 燃烧温度(K) | 产气量(mol/100g) | 产生的CO的量(mol/100g) | 产生的NO的量(mol/100g) | |
实施例1 | 蜜胺/BCN=20.8/79.2 | 1503 | 2.14 | 2.5×10-4 | 0 |
实施例2 | 蜜胺/BCN/CMCNa=18.8/78.2/3 | 1463 | 2.16 | 3.6×10-2 | 0 |
实施例3 | 蜜胺/BCN/CMCNa=20.8/76.2/3 | 1358 | 2.28 | 0.12 | 0 |
实施例4 | 蜜胺/BCN/Gum=18.51/78.49/3 | 1449 | 2.17 | 3.5×10-2 | 0 |
实施例5 | 蜜胺/BCN/CMCNa/Al(OH)3=17.76/74.24/3/5 | 1358 | 2.15 | 3.1×10-2 | 0 |
实施例6 | 蜜胺/BCN/CMCNa/Al(OH)3=16.72/70.28/3/10 | 1292 | 2.14 | 2.8×10-2 | 0 |
实施例7 | 蜜胺/BCN/CMCNa/Al(OH)3=15.68/66.32/3/15 | 1177 | 2.13 | 2.2×10-2 | 0 |
实施例8 | 蜜胺/BCN/CMCNa/Co3O4=17.99/74.01/3/5 | 1423 | 2.06 | 3.5×10-2 | 0 |
实施例9 | 蜜胺/BCN/CMCNa/Co3O4=17.18/69.82/3/10 | 1382 | 1.97 | 3.3×10-2 | 0 |
实施例10 | 蜜胺/BCN/Gum/Al(OH)3=17.47/74.53/3/5 | 1358 | 2.16 | 3.1×10-2 | 0 |
实施例11 | 蜜胺/BCN/Gum/Al(OH)3=16.43/70.57/3/10 | 1281 | 2.15 | 2.7×10-2 | 0 |
实施例12 | 蜜胺/BCN/Gum/Al(OH)3=15.39/66.61/3/15 | 1166 | 2.14 | 2.2×10-2 | 0 |
实施例13 | 蜜胺/BCN/Gum/CO3O4=17.70/74.30/3/5 | 1408 | 2.07 | 3.4×10-2 | 0 |
实施例14 | 蜜胺/BCN/Gum/CO3O4=16.89/70.11/3/10 | 1367 | 1.99 | 3.3×10-2 | 0 |
实施例15 | THT/BCN=23.40/76.60 | 1786 | 2.28 | 3.3×10-3 | 7.2×10-5 |
实施例16 | THT/BCN/CMCNa=20.40/76.60/3 | 1749 | 2.24 | 2.4×10-3 | 2.5×10-5 |
实施例17 | THT/BCN/Gum=20.00/77.00/3 | 1739 | 2.24 | 1.2×10-3 | 4.5×10-5 |
实施例18 | THT/BCN/Gum/Al(OH)3=18.9/73.1/3/5 | 1603 | 2.23 | 1.8×10-3 | 3.1×10-6 |
比较例1 | BHTK/KNO3=51.44/48.56 | 2393 | 1.26 | 5.1×10-4 | 4.1×10-3 |
比较例2 | NaN3/CuO=61/39 | 1421 | 1.41 | 0 | 1.3×10-6 |
实施例1-18中的燃烧温度都比比较例1的非叠氮基产气剂的低600度以上,实施例3、5-7和9-14的燃烧温度甚至比比较例2的叠氮基产气剂的要低。另外,在实施例1-14中,理论上不出现NO,且发现相对于比较例1和2有降低产生的NO的量的效果。另外,实施例1-18的产气量高出比较例2的叠氮基产气剂超过50%。
实施例19-24
制备每个具有表2所示配方的产气组合物。根椐JISK 4810-1979爆破性能测试法,测试这些组合物的摩擦敏感性和落锤敏感性。测试结果列于表2。
表2
配方(重量%) | 摩擦敏感性(kgf) | 落锤敏感性(cm) | |
实施例19 | 蜜胺/BCN/CMCNa=19.80/77.20/3 | >36.0 | >100 |
实施例20 | 蜜胺/BCN/CMCNa/Co3O4=17.18/69.82/3/10 | >36.0 | >100 |
实施例21 | 蜜胺/BCN/CMCNa/Al(OH)3=16.72/70.28/3/10 | >36.0 | >100 |
实施例22 | 蜜胺/BCN/CMCNa/Japanese acidclay=20.80/76.20/3/5 | >36.0 | >100 |
实施例23 | 蜜胺/BCN/CMCNa/SiO2=20.80/76.20/3/5 | >36.0 | >100 |
实施例24 | 蜜胺/BCN/CMCNa/mica=20.80/76.20/3/5 | >36.0 | >100 |
在实施例19-24中,摩擦敏感性超过36.0kgf,落锤敏感性超过100cm。因此,认为处理的安全性很高。
实施例25-30
制备每个具有表3所示配方的产气组合物。对这些组合物,用RigakuK,K制造的TAS型差热分析仪测量熔化温度、开始热分解的温度、和开始TG重量损失的温度。在测试中温度升高的速率为20℃/分,测试的气氛为氮气,测试中样品的量为1-2mg。结果示于表3中。
表3
配方(重量%) | 熔化温度(℃) | 开始热分解的温度(℃) | 开始重量损失的温度(℃) | |
实施例25 | 蜜胺/BCN=25/75 | 210 | 237 | 230 |
实施例26 | 蜜胺/BCN/CMCNa=20.80/76.20/3 | 206 | 233 | 214 |
实施例27 | 蜜胺/BCN/CMCNa/Co3O4=17.18/69.82/3/10 | 203 | 229 | 211 |
实施例28 | 蜜胺/BCN/CMCNa/Al(OH)3=16.72/70.28/3/10 | 204 | 231 | 212 |
实施例29 | THT/BCN=23.4/76.6 | - | 180 | 185 |
实施例30 | THT/BCN/CMCNa=20.4/76.6/3 | - | 179 | 182 |
在实施例25-30中,发现熔化温度、开始热分解的温度、和开始重量损失的温度足够高且热稳定性好。
实施例31-35
制备每个具有表4所示配方的产气组合物。把这些组合物每一个模制成绳。在氮气氛下在4900、6860或8820kPa的压力下测试燃烧速率。在6860kPa和4900-8280kPa的压力指数下的燃烧速率示于表4中。
表4
配方(重量%) | 燃烧速率(mm/秒) | 压力指数 | |
实施例31 | 蜜胺/BCN/CMCNa=19.80/77.20/3 | 15.89 | 0.25 |
实施例32 | 蜜胺/BCN/CMCNa/Co3O4=17.99/74.01/3/5 | 15.26 | 0.18 |
实施例33 | 蜜胺/BCN/CMCNa/Co3O4=17.18/69.82/3/10 | 14.03 | 0.16 |
实施例34 | 蜜胺/BCN/Gum/Al(OH)3=17.47/74.53/3/5 | 13.98 | 0.18 |
实施例35 | 蜜胺/BCN/Gum/Al(OH)3=16.43/70.57/3/10 | 10.15 | 0.20 |
实施例31-35中所示的各个值表明这些组合物满足作为充气机的产气组合物的实际要求。
实施例36-48
制备每个具有表5所示配方的产气组合物。把这些组合物每一个模制成2g的绳。把该绳安装在内容积为1升的封闭的弹内,并把弹内用氮气冲洗。从镍铬合金通电流来点燃此绳,并完全燃烧。通电流开始起20秒后,在气体抽样袋中收集气体,用探测管立即分析NO2、NO、CO和CO2的浓度。
表5
配方(重量%) | 产生的NO2的量ppm | 产生的NO的量ppm | 产生的CO的量ppm | 产生的CO2的量ppm | |
实施例36 | 蜜胺/BCN=20.8/79.2 | 0 | 37 | 50 | 2300 |
实施例37 | 蜜胺/BCN/CMCNa=18.8/78.2/3 | 0 | 55 | 110 | 3000 |
实施例38 | 蜜胺/BCN/CMCNa=19.8/77.2/3 | 0 | 42 | 150 | 1700 |
实施例39 | 蜜胺/BCN/CMCNa=20.8/76.2/3 | 0 | 9 | 130 | 1400 |
实施例40 | 蜜胺/BCN/CMCNa/Al(OH)3=17.76/74.24/3/5 | 0 | 8 | 100 | 1700 |
实施例41 | 蜜胺/BCN/CMCNa/Al(OH)3=15.72/71.28/3/10 | 0 | 13 | 70 | 1900 |
实施例42 | 蜜胺/BCN/CMCNa/Al(OH)3=16.72/70.28/3/10 | 0 | 6 | 130 | 2100 |
实施例43 | 蜜胺/BCN/CMCNa/Al(OH)3=17.72/69.28/3/10 | 0 | 4 | 160 | 1700 |
实施例44 | 蜜胺/BCN/CMCNa /Al(OH)3=15.68/66.32/3/15 | 0 | 5 | 100 | 1700 |
实施例45 | 蜜胺/BCN/CMCNa/Co3O4=17.99/74.01/3/5 | 0 | 30 | 110 | 1500 |
实施例46 | 蜜胺/BCN/CMCNa/Co3O4=17.18/69.82/3/10 | 0 | 9 | 120 | 1400 |
实施例47 | 蜜胺/BCN/CMCNa/Japanese acidclay=20.8/76.2/3/5 | 0 | 17 | 170 | 2100 |
实施例48 | 蜜胺/BCN/CMCNa/mica=20.8/76.2/3/5 | 0 | 5 | 220 | 2100 |
Claims (17)
1、一种包括(a)三嗪化合物和(b)含氧氧化剂的产气组合物,其中组分(b)的氧化剂是选自金属过酸和碱式金属硝酸盐中的至少一种,其中碱式金属硝酸盐是选自碱式硝酸铜、碱式硝酸钴、碱式硝酸锌、碱式硝酸锰、碱式硝酸铁、碱式硝酸钼、碱式硝酸铋和碱式硝酸铈的至少一种。
2、权利要求1的组合物,其中(a)三嗪化合物是选自三嗪化合物、蜜胺化合物、三肼基三嗪、三羟甲基蜜胺、烷基化羟甲基蜜胺、三聚氰酸二酰胺、三聚氰酸一酰胺、ammelande、氰尿酸、氰尿酸化合物、蜜白胺、蜜勒胺、硝酸蜜胺、高氯酸蜜胺、和硝基蜜胺中的至少一种。
3、权利要求1或2的组合物,其包括5-60%重量的组分(a)和40-95%重量的组分(b)。
4、权利要求1-3中任一项的组合物,其还包括(c)粘合剂和/或(d)添加剂。
5、权利要求4的组合物,其中(c)粘合剂是选自下列的至少一种:羧甲基纤维素、羧甲基纤维素钠盐、羧甲基纤维素的钾盐、羧甲基纤维素的铵盐、乙酸纤维素、乙酸丁酸纤维素、甲基纤维素、乙基纤维素、羟乙基纤维素、乙基羟乙基纤维素、羟丙基纤维素、羧甲基乙基纤维素、细结晶纤维素、聚丙烯酰胺、聚丙烯酰胺的胺产品、聚丙烯酰肼、丙烯酸酰胺和丙烯酸的金属盐的共聚物、聚丙烯酸酰胺和聚丙烯酸酯的共聚物、聚乙烯醇、丙烯酸酯橡胶、瓜尔胶、淀粉、硅氧烷。
6、权利要求4的组合物,其中(d)添加剂是选自下列的至少一种:选自氧化铜、氧化铁、氧化锌、氧化钴、氧化锰、氧化钼、氧化镍、氧化铋、氧化硅和氧化铝的金属氧化物;选自氢氧化铝、氢氧化钴和氢氧化铁的金属氢氧化物;选自碳酸钴、碳酸钙、碱式碳酸锌和碱式碳酸铜的金属碳酸盐或碱式金属碳酸盐;选自日本酸性粘土、高岭土、滑石、膨润土、硅藻土、水滑石的金属氧化物和氢氧化物的复合物;选自硅酸钠、云母、钼酸盐、钼酸钴和钼酸铵的金属酸盐;硅氧化物、二硫化钼、硬脂酸钙、氮化硅和碳化硅。
7、权利要求4、5和6中任一项的组合物,其包括0.1-15%重量的组分(c)和0.1-20%重量的组分(d)。
8、权利要求1-7中任一项的组合物,其中组分(a)是蜜胺或三肼基三嗪,组分(b)是碱式硝酸铜。
9、权利要求8的组合物,其包括15-45%重量的(a)蜜胺或三肼基三嗪和55-85%重量的(b)碱式硝酸铜。
10、权利要求4的组合物,其包括(a)蜜胺或三肼基三嗪,(b)碱式硝酸铜和(c)羧甲基纤维素钠或瓜尔胶。
11、权利要求10的组合物,其包括15-25%重量的(a)蜜胺、60-80%重量的(b)碱式硝酸铜和0.1-10%重量的(c)羧甲基纤维素钠或瓜尔胶。
12、权利要求10的组合物,其包括15-25%重量的(a)三肼基三嗪、60-80%重量的(b)碱式硝酸铜和0.1-10%重量的(c)羧甲基纤维素钠或瓜尔胶。
13、权利要求7的组合物,其包括15-25%重量的(a)蜜胺、60-80%重量的(b)碱式硝酸铜和0.1-10%重量的(c)羧甲基纤维素钠和1-15%重量的(d)氢氧化铝或1-10%重量的(d)氧化钴。
14、权利要求7的组合物,其包括10-25%重量的(a)三肼基三嗪、60-80%重量的(b)碱式硝酸铜和0.1-10%重量的(c)羧甲基纤维素钠1-15%重量的(d)氢氧化铝或1-10%重量的(d)氧化钴。
15、由挤出权利要求1-14中任一项的产气组合物而得到的呈单孔柱状或多孔柱状的产气组合物的模制件。
16、由压塑权利要求1-14中任一项的产气组合物而得到的呈粒状的产气组合物的模制件。
17、使用权利要求1-14中任一项的产气组合物的用于气囊的充气机。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP27647/2000 | 2000-02-04 | ||
JP2000027647A JP4500399B2 (ja) | 2000-02-04 | 2000-02-04 | トリアジン誘導体を含むガス発生剤組成物 |
Publications (2)
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CN1398244A CN1398244A (zh) | 2003-02-19 |
CN1210234C true CN1210234C (zh) | 2005-07-13 |
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CNB018045464A Expired - Lifetime CN1210234C (zh) | 2000-02-04 | 2001-02-01 | 含有三嗪衍生物的产气组合物 |
Country Status (7)
Country | Link |
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US (1) | US20030024618A1 (zh) |
EP (1) | EP1254880B1 (zh) |
JP (1) | JP4500399B2 (zh) |
KR (1) | KR100838192B1 (zh) |
CN (1) | CN1210234C (zh) |
TW (1) | TWI231809B (zh) |
WO (1) | WO2001056953A1 (zh) |
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JP4610266B2 (ja) * | 2004-09-09 | 2011-01-12 | ダイセル化学工業株式会社 | ガス発生剤組成物 |
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-
2000
- 2000-02-04 JP JP2000027647A patent/JP4500399B2/ja not_active Expired - Lifetime
-
2001
- 2001-02-01 WO PCT/JP2001/000711 patent/WO2001056953A1/ja active Application Filing
- 2001-02-01 KR KR1020027009801A patent/KR100838192B1/ko active IP Right Grant
- 2001-02-01 EP EP01948976.4A patent/EP1254880B1/en not_active Expired - Lifetime
- 2001-02-01 CN CNB018045464A patent/CN1210234C/zh not_active Expired - Lifetime
- 2001-02-01 US US10/181,781 patent/US20030024618A1/en not_active Abandoned
- 2001-02-01 TW TW090102015A patent/TWI231809B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
US20030024618A1 (en) | 2003-02-06 |
EP1254880A1 (en) | 2002-11-06 |
JP2001220282A (ja) | 2001-08-14 |
KR100838192B1 (ko) | 2008-06-16 |
EP1254880B1 (en) | 2019-09-04 |
JP4500399B2 (ja) | 2010-07-14 |
EP1254880A4 (en) | 2011-01-26 |
TWI231809B (en) | 2005-05-01 |
CN1398244A (zh) | 2003-02-19 |
KR20020071028A (ko) | 2002-09-11 |
WO2001056953A1 (fr) | 2001-08-09 |
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