EP1798318B1 - Flammhemmende synthetische faser, flammhemmender faserkomposit sowie damit hergestelltes polstermöbel - Google Patents
Flammhemmende synthetische faser, flammhemmender faserkomposit sowie damit hergestelltes polstermöbel Download PDFInfo
- Publication number
- EP1798318B1 EP1798318B1 EP05770521A EP05770521A EP1798318B1 EP 1798318 B1 EP1798318 B1 EP 1798318B1 EP 05770521 A EP05770521 A EP 05770521A EP 05770521 A EP05770521 A EP 05770521A EP 1798318 B1 EP1798318 B1 EP 1798318B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- fiber
- parts
- compound
- flame
- 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.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 256
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229920002994 synthetic fiber Polymers 0.000 title claims abstract description 34
- 239000012209 synthetic fiber Substances 0.000 title claims abstract description 34
- 239000003063 flame retardant Substances 0.000 title description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title description 3
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 33
- 125000005843 halogen group Chemical group 0.000 claims abstract description 32
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 31
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000004745 nonwoven fabric Substances 0.000 claims description 99
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 70
- 229910052736 halogen Inorganic materials 0.000 claims description 68
- 150000002367 halogens Chemical class 0.000 claims description 68
- 229920000728 polyester Polymers 0.000 claims description 39
- 239000011787 zinc oxide Substances 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 34
- 239000005995 Aluminium silicate Substances 0.000 claims description 32
- 235000012211 aluminium silicate Nutrition 0.000 claims description 32
- 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 32
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 17
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000011667 zinc carbonate Substances 0.000 claims description 7
- 235000004416 zinc carbonate Nutrition 0.000 claims description 7
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 150000002681 magnesium compounds Chemical class 0.000 claims description 6
- 235000010755 mineral Nutrition 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000010451 perlite Substances 0.000 claims description 6
- 235000019362 perlite Nutrition 0.000 claims description 6
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 235000012216 bentonite Nutrition 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 235000012222 talc Nutrition 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004753 textile Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 238000011156 evaluation Methods 0.000 description 85
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 44
- 235000014692 zinc oxide Nutrition 0.000 description 37
- 238000012360 testing method Methods 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 32
- 239000004744 fabric Substances 0.000 description 29
- 238000002485 combustion reaction Methods 0.000 description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
- 239000000654 additive Substances 0.000 description 19
- 229940024545 aluminum hydroxide Drugs 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 15
- 229920000297 Rayon Polymers 0.000 description 14
- 239000006260 foam Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000002964 rayon Substances 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- OWOMRZKBDFBMHP-UHFFFAOYSA-N zinc antimony(3+) oxygen(2-) Chemical compound [O--].[Zn++].[Sb+3] OWOMRZKBDFBMHP-UHFFFAOYSA-N 0.000 description 9
- 241000219146 Gossypium Species 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000009960 carding Methods 0.000 description 6
- 239000012210 heat-resistant fiber Substances 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 polyethylenes Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 235000016804 zinc Nutrition 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 4
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical class Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- CSZMVWXOMQAQJM-UHFFFAOYSA-N 1,1-dichloroethene;1,1-difluoroethene;prop-2-enenitrile Chemical compound C=CC#N.FC(F)=C.ClC(Cl)=C CSZMVWXOMQAQJM-UHFFFAOYSA-N 0.000 description 1
- QLUXVUVEVXYICG-UHFFFAOYSA-N 1,1-dichloroethene;prop-2-enenitrile Chemical compound C=CC#N.ClC(Cl)=C QLUXVUVEVXYICG-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- 241000282836 Camelus dromedarius Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000004221 Multiple Trauma Diseases 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 244000044822 Simmondsia californica Species 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RQPPGNOSTFLTRU-UHFFFAOYSA-N bromoethene;1,1-dichloroethene;prop-2-enenitrile Chemical compound BrC=C.C=CC#N.ClC(Cl)=C RQPPGNOSTFLTRU-UHFFFAOYSA-N 0.000 description 1
- UANXTELADQKHSM-UHFFFAOYSA-N bromoethene;chloroethene;prop-2-enenitrile Chemical compound ClC=C.BrC=C.C=CC#N UANXTELADQKHSM-UHFFFAOYSA-N 0.000 description 1
- RMGATEFMKWDUPT-UHFFFAOYSA-N bromoethene;prop-2-enenitrile Chemical compound BrC=C.C=CC#N RMGATEFMKWDUPT-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- YZIPEAHOHOYNCE-UHFFFAOYSA-N chloroethene;1,1-dichloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N.ClC(Cl)=C YZIPEAHOHOYNCE-UHFFFAOYSA-N 0.000 description 1
- GRFFKYTUNTWAGG-UHFFFAOYSA-N chloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N GRFFKYTUNTWAGG-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- ANENMIYXPMTPHB-UHFFFAOYSA-N fluoroethene;prop-2-enenitrile Chemical compound FC=C.C=CC#N ANENMIYXPMTPHB-UHFFFAOYSA-N 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
Definitions
- the present invention relates to a flame resistant synthetic fiber having advanced flame resistance preferably usable for textiles, to a flame resistant fiber composite, and a nonwoven fabric comprising the flame resistant fiber composite, usable for furniture that needs advanced flame resistance, such as bedding as bed mattress, chairs, and sofa, the fiber being rendered highly flame resistant with flame resistant agents, also having extremely high carbonizability. Furthermore, the present invention relates to upholstered furniture products using them.
- flammable materials such as cotton, polyesters, urethane foams
- flammable materials such as cotton, polyesters, urethane foams
- the flame resisting materials must not impair comforts or sensuousness of the products of these beddings and furniture.
- flammable materials such as cotton, urethane foams, polyesters
- these textiles for comfort during use, important is flame retardation covering over a long period of time for preventing flaming to the flammable materials.
- the flame retardant material must not impair comforts or sensuousness of furniture, such as beddings or chairs, and of mattresses, and sofas.
- polyesters cannot exhibit functions as a carbonizable component, they induce melting and perforation by power burner combustion.
- Use of inexpensive polyester materials induces flaming to cottons and urethane foams used for the above-mentioned beddings, furniture, etc., and disables maintenance of structure of the materials, resulting in completely inadequate performance.
- cloths from organic heat-resistant fibers are excellent in flame resistance, they are extremely expensive, and have further problems of workability in filament opening poor moisture absorptivity or touch, and difficulty in highly designed colored patterns resulting from poor dyestuff affinity.
- organic heat-resistant fibers are generally colored resulting in inadequate whiteness of fabrics. Further organic heat-resistant fibers have problems in coloring during dyeing process. Therefore the composite has problems in sensuousness.
- the present invention aims at solving problems that have been difficult to be solved by conventional flame resistant materials. That is, the present invention aims at obtaining a flame resistant synthetic fiber with satisfactory workability, touch, and feeling, and furthermore satisfactory sensuousness, being suitably used for upholstered furniture products, a flame resistant fiber composite, and nonwoven fabric comprising the flame resistant fiber composite, and furthermore upholstered furniture products using the composite.
- the present inventors found out that simultaneous inclusion of zinc compounds selected from zinc, zinc oxide, and zinc carbonate, antimony compounds, and other inorganic compounds as specified in claim 1, in a flame resistant synthetic fiber having a content of halogen of not less than 17% by weight might enable acquisition of advanced flame resistance.
- a flame resistant synthetic fiber for providing textiles, usable for furniture, bedding, etc., having flame resistance with prolonged durability to flame, and self-extinguishing property without impairing sensuousness might be obtained at low costs.
- problems of workability in use in independent use of a heat-resistant fiber, and of price might be improved, leading to completion of the present invention.
- the present invention is a flame resistant fiber composite consisting of:
- the polymer containing halogen atom of not less than 17% by weight is preferably a flame resistant synthetic fiber (A) consisting of:
- the zinc compound contained in the flame resistant synthetic fiber (A) is a compound selected from a group consisting of zinc, zinc oxide, and zinc carbonate.
- the inorganic compound is a compound selected from a group consisting of natural or synthetic mineral based compounds, such as kaolin, zeolite, montmorillonite, talc, perlite, bentonite, vermiculite, diatomaceous earth, and graphite; aluminum based compounds, such as aluminum hydroxide, aluminum sulfate, and aluminum silicate; magnesium compounds, such as magnesium hydroxide and magnesium oxide; and silicon compounds, such as silicate and glasses.
- natural or synthetic mineral based compounds such as kaolin, zeolite, montmorillonite, talc, perlite, bentonite, vermiculite, diatomaceous earth, and graphite
- aluminum based compounds such as aluminum hydroxide, aluminum sulfate, and aluminum silicate
- magnesium compounds such as magnesium hydroxide and magnesium oxide
- silicon compounds such as silicate and glasses.
- the present invention relates to a flame resistant fiber composite using the flame resistant synthetic fiber (A) and a polyester fiber especially a binder fiber having a low melting point 0 to 40 parts by weight, as the natural fiber and/or the chemical fiber (B).
- the present invention further relates to a nonwoven fabric comprising the flame resistant fiber composites, and especially to a nonwoven fabric for flame shielding barriers, and furthermore to upholstered furniture products using these flame resistant fiber composites, nonwoven fabrics, and nonwoven fabric for flame shielding barriers.
- a fiber (A) as used herein for a flame resistant fiber composite means the above described flame resistant synthetic fiber.
- the flame resistant synthetic fiber composite of the present invention and interior designed textile product thereof have outstanding sensuousness, such as touch, feeling, and visual appreciation, and also workability, and it enables demonstration of advanced flame resistance by maintaining a fiber form thereof against touch to a flame for a long period of time.
- a preferable minimum amount of halogen content in the polymer containing halogen atom of not less than 17% of the present invention is 20%, and more preferably it is 26%.
- a preferable maximum amount is 86%, more preferably it is 73%, and still more preferably 48%.
- a halogen content of vinylidene bromide homopolymers has a value of 86%, this value makes a maximum value of halogen content. In order to obtain halogen content not less than this value, it is necessary to further increase halogen atoms in a monomer, therefore becoming technically less realistic.
- the polymer containing halogen atom of not less than 17% includes, but not limited to, for example, polymers of a monomer containing halogen atom, copolymers of the monomer containing halogen atom and monomers without halogen atom, mixtures of a polymer containing halogen atom, and a polymer without halogen atom, and halogen atom containing polymers having halogen atom introduced during or after polymerization of monomers without halogen atom or polymer etc.
- polymers containing halogen atom of not less than 17% by weight include, but not limited to, for example, homopolymers of halogen containing vinyl based or vinylidene based monomers or copolymers obtained from two or more kinds the monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, and vinylidene fluoride; copolymers of halogen containing vinyl based or vinylidene based monomers, and acrylonitrile, such as acrylonitrile-vinyl chloride, acrylonitrile- vinylidene chloride, acrylonitrile-vinyl bromide, acrylonitrile-vinyl fluoride, acrylonitrile-vinyl chloride-vinylidene chloride, acrylonitrile-vinyl chloride-vinyl bromide, acrylonitrile-vinylidene chloride-vinyl bromide and acrylonitrile-
- the vinyl monomers copolymerizable with the monomers include acrylic acid, esters thereof, methacrylic acid, esters thereof, acrylamide, methacryl amide, vinyl acetate, vinyl sulfonic acid, salts thereof, methallyl sulfonic acid, salts thereof, styrene sulfonic acid, salts thereof, 2-acrylamide-2-methylpropanesulfcnic acid, salts thereof etc., and they may be used independently or two or more kinds may be used in combination. When at least one kind of them is a sulfonic group containing vinyl monomer, dyestuff affinity preferably will improve.
- the vinyl monomers copolymerizable with the monomers include acrylic acid, esters thereof, methacrylic acid, esters thereof, acrylamide, methacryl amide, vinyl acetate, vinyl sulfonic acid, salts thereof, methallyl sulfonic acid, salts thereof, styrene sulfonic acid, salts thereof, 2-acrylamide-2-methylpropanesulfonic acid, salts thereof etc., and they may be used independently or two or more kinds may be used in combination. When at least one kind is a sulfonic group containing vinyl monomer among them, dyestuff affinity preferably will improve.
- copolymer including the halogen containing vinyl based monomer and/or halogen containing vinylidene monomer and a unit from acrylonitrile examples include, for example, a copolymer consisting of vinyl chloride 50 parts, acrylonitrile 49 parts, and sodium styrene sulfonate 1 part; a copolymer consisting of vinylidene chloride 47 parts, acrylonitrile 51.5 parts, and sodium styrene sulfonate 1.5 parts; and a copolymer consisting of vinylidene chloride 41 parts, acrylonitrile 56 parts, and 3 part of sodium 2-acrylamide-2-methylsulfonate etc. These copolymers can be obtained by conventionally known polymerization methods.
- Zinc compounds used for the present invention are selected from zinc, zinc oxide, and zinc carbonate. They may be used independently and combination of them may also be used.
- An amount to be used is 3 to 50 parts by weight to the polymer containing halogen atom of not less than 17% 100 parts by weight, preferably it is 4 to 40 parts by weight, and more preferably 5 to 30 parts by weight.
- An amount of less than 3 parts by weight to be used tends to reduce effect (carbonizing effect) of carbonizing the polymer containing halogen atom of not less than 17% at the time of combustion, and cannot provide necessary carbonizing effect for providing requested advanced flame resistance.
- An amount used exceeding 50 parts by weight may provide sufficient carbonizing effect and form maintenance effect, but undesirably generates yarn breakage etc.
- an average particle diameter of the zinc compounds is preferably not more than 3 micrometers.
- the zinc compound component may further have chemical modification onto particle surface thereof for improvement in blocking property.
- antimony compounds include inorganic antimony compounds as follows, but not limited to, antimony oxide compounds, such as antimony trioxide, antimony tetroxide, and antimony pentoxide; antimonic acid and salts thereof; antimony oxychloride etc. They may be used independently and combination of them may also be used An amount to be used is 0 to 30 parts by weight to the polymer containing halogen atom of not less than 17% 100 parts by weight, preferably it is 0 to 25 parts by weight, and more preferably 0 to 20 parts by weight. An amount to be used exceeding 30 parts by weight saturates the effect, and undesirably causes increase in costs.
- antimony oxide compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide
- antimonic acid and salts thereof antimony oxychloride etc.
- antimony oxychloride etc. They may be used independently and combination of them may also be used
- An amount to be used is 0 to 30 parts by weight to the
- Examples of the inorganic compounds are selected from natural or synthetic mineral product based compounds, such as kaolin, zeolite, montmorillonite, talc, perlite, bentonite, vermiculite, diatomaceous earth, and graphite; aluminum based compounds, such as aluminum hydroxide, aluminum sulfate, and aluminum silicate; magnesium compounds, such as magnesium hydroxide and magnesium oxide; and silicon compounds, such as silicates and glasses etc. They may be used independently and combination of them may also be used.
- An amount is 3 to 30 parts by weight to polymers containing halogen atom of not less than 17 100 parts by weight, it is preferably 5 to 25 parts by weight, and more preferably 7 to 20 parts by weight.
- An amount of less than 3 parts by weight gives only a small amount of residual carbide at the time of combustion, and thereby fails to demonstrate sufficient form maintenance effect.
- An amount exceeding 30 parts by weight saturates desired effect, gives factor of increase in costs, and disadvantageously causes trouble occurrence, such as nozzle clogging on manufacturing process of the fiber.
- a total amount of the previously described zinc compounds, antimony compounds, and other inorganic compounds is not less than 15 parts by weight and not more than 110 parts by weight to the polymer containing halogen atom of not less than 17% 100 parts by weight, preferably it is not less than 17 parts by weight and is not more than 70 parts by weight, and more preferably not less than 20 parts by weight and not more than 50 parts by weight. It is disadvantageously difficult for an amount of the additives of less than 15 parts by weight to give previously described advanced flame resisting effect.
- a flame resistant synthetic fiber of the present invention may include other additives, such as antistatic agents, agents for prevention of coloring by heat, light resistance improvers, whiteness improvers, matting inhibitors, colorants, and flame resistant agents, if necessary.
- a flame resistant synthetic fiber of the present invention may be manufactured using polymers containing halogen atom of not less than 17% by weight, using publicly known manufacturing methods, such as a wet spinning method, a dry spinning method, and a half-dry half-wet method.
- a wet spinning method after dissolving the polymer in solvents, such as N,N-dimethylformamide, N,N-dimethylacetamide, acetone, and rhodan salt aqueous solution, an obtained solution is extruded and coagulated in a coagulation bath through nozzles, subsequently, obtained fibers are washed, dried, stretched and heat-treated, and then the fibers will be crimped and cut if necessary, obtaining a desired product.
- solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetone, and rhodan salt aqueous solution
- solvents such as N,N-dimethylformamide, N,N-di
- a form of the flame resistant synthetic fiber of the present invention may be of staple fiber or may be of filament, and may be appropriately selected based on application for use.
- a similar form as of a partner fiber is preferable in processing by means of compounding with other natural fibers and chemical fibers.
- a staple fiber having approximately 1.7 to 12 dtex and approximately a cut length of 38 to 128 mm is preferable.
- a flame resistant synthetic fiber of the present invention to exhibit excellent flame resistance is considered as follows.
- a fiber (A) as specified in claim 1 containing a zinc compound 3 to 50 parts by weight, an antimony compound 0 to 30 parts by weight, and an other inorganic compound 3 to 30 parts by weight to a polymer containing halogen atom of not less than 17% 100 part by weight is made to burn by other sources of flame, halogen atoms in a polymer decomposed by combustion of the polymer first easily react with a zinc compound and an antimony compound contained in a fiber (A) to form zinc chloride and antimony chloride compounds, and, when an antimony compound is not included, to form hydrogen chloride.
- the zinc chloride works as a catalyst of chain cross-link reaction in the polymer, chains in the polymer are mutually cross-linked during combustion, resulting in formation of solid carbides (carbonizing effect).
- the antimony chloride compound or hydrogen chloride is a low boiling compound and a gas thereof is incombustible, oxygen of a combustion area is blocked out, and thereby combustion is suppressed, resulting in demonstration of fire extinguishing action (self-extinguishing effect).
- the other inorganic compound is not completely reduced to ashes at the time of combustion, the inorganic compound remains within the carbides, when above described solid carbide is formed, thereby increasing strength of the carbides (form maintenance effect).
- the fiber (A) may have combination of the carbonizing effect, the self-extinguishing effect, and the form maintenance effect, and may maintain a form in a state of carbides, without fiber form collapse even after combustion. Moreover, since the fiber (A) has the self-extinguishing effect, a flame is blocked out and spread of a fire may be suppressed, therefore demonstrating excellent flame resistance.
- Natural fibers and/or chemical fibers (B) used for the present invention are components for giving a flame resistant fabric of the present invention outstanding touch, feeling, sensuousness, product strength, washing resistance, and durability in use, and they are also components for satisfactorily improving workability at time of using a flame resistant nonwoven fabric for beddings or furniture.
- Examples of the natural fiber include, but not limited to, vegetable fibers, such as cotton and hemp; animal fibers, such as wool, camel hair, goat hair, and silk etc.
- examples of chemical fiber include, regenerated fibers, such as viscose rayon fibers and cuprammonium rayon fibers; regenerated fiber, such as acetate fibers; and synthetic fibers, such as nylon fibers, polyester fibers, polyester based low melting point binder fibers, and acrylic fibers.
- These natural fibers and chemical fibers may be independently used with the flame resistant synthetic fiber (A), and two or more kinds may be used in combination with the flame resistant synthetic fiber (A).
- polyesters of 15 to 25 parts by weight as B in a whole of (A + B) 100 parts by weight may be included, because the polyester fiber generates fused materials at the time of combustion to cover a flame resistant nonwoven fabric and thereby to strengthen a carbonized layer formed of the flame resistant nonwoven fabric, and also the polyester fiber can give flame shielding barrier performance for preventing flaming to cotton materials and urethane foam materials used for beddings or furniture, in prolonged exposure to intense flame; because the polyester fiber easily give bulkiness in processing into a nonwoven fabric; and because the polyester fiber may suppress a problem of damaging fibers due to a weak strength of a halogen containing synthetic fiber in a hopper feeder (carding device).
- polyester based low melting point binder fibers enables adoption of a simpler thermo-fusible adhesion method in the case of manufacturing of nonwoven fabric.
- polyester based low melting point binder fiber may also include a low melting point polyester single type fiber, and may include conjugate fibers of parallel connected type or core-in-sheath type consisting of (polyester) / (low melting point polypropylene, low melting point polyethylene, and low melting point polyester).
- low melting point polyesters have a melting point of almost 110 to 200 degree C
- low melting point polypropylenes have a melting point of almost 140 to 160 degree C
- low melting point polyethylene have a melting point of almost 95 to 130 degree C
- the materials are not especially limited, if they demonstrate fusible adhesion capability at temperatures about 110 to 200 degree C.
- use of polyester fibers without low melting points allows adoption of simpler needle punch methods in manufacture of the nonwoven fabric.
- a flame resistant fabric 100 parts by weight of the present invention may be manufactured from a flame resistant synthetic fiber (A) not less than 10 parts by weight, and a natural fiber and/or a chemical fiber (B) not more than 90 parts by weight. Blending ratios of the material fibers here are determined according to quality, such as flame resistance needed for final products manufactured from a flame resistant nonwoven fabric obtained, and moreover absorptivity, touch, moisture absorptivity, feeling, sensuousness, product strength, washing resistance, and durability in use.
- the synthetic fiber (A) 95 to 10 parts by weight, and preferably 60 to 20 parts by weight, the natural fiber and/or chemical fiber (B) 5 to 90 parts by weight, preferably 80 to 40 parts by weight are used to be compounded so that this total amount may give 100 parts by weight.
- the thermo-fusible adhesion method in the case of the nonwoven fabric manufacturing process, inclusion of the polyester based low melting point binder fiber of at least 10 parts by weight is preferable as the natural fiber and/or chemical fiber (B).
- An amount of less than 10 parts by weight of the flame resistant synthetic fiber (A) fails to realize enough formation of carbonized layer for preventing flaming to cotton and urethane foams used for beddings or furniture on the occasion of prolonged exposure to intense flame, and may only demonstrate poor self-extinguishing property, making it difficult to realize requested advanced flame resistance.
- the previously described fibers (A) and (B) are compounded, and the flame resistant fiber composite has a form of: fabrics, such as woven or knitted fabrics and nonwoven fabrics; collection of fibers, such as slivers and webs; fibrous materials, such as spun yarns, multiple wound yarns, twisted yarns; and corded materials, such as knitted strings and plaited cords.
- the above-described "compound” as used herein means that the fibers (A) and (B) are mixed by various methods to obtain a fabric including the fibers (A) and (B) at a predetermined ratio, and also that each fibers and yarns are combined in stages of blending, spinning, twisting, weaving and knitting.
- a flame resistant fiber composite of the present invention may suitably be used as a nonwoven fabric for flame shielding barriers.
- Flame shielding barrier as used herein means that when a flame resistant nonwoven fabric is exposed to flame, it shields against the flame by carbonizing itself, while maintaining a form of the fiber in an inflammable nonwoven fabric, to prevent the flame moving to an opposite side of the woven fabric.
- interposition of the flame resistant nonwoven fabric of the present invention between a fabric disposed outside of mattress and upholstered furniture etc., and urethane foam or packing as an internal structure etc. can prevent catching of a flame to internal structure in case of contacting flame, thereby giving least damage.
- nonwoven fabric preparation methods such as a general thermofusible adhesion method, a chemical bonding method, a water jet method, a needle punch method, and a stitch bonding method, may be used.
- a general thermofusible adhesion method such as a general thermofusible adhesion method, a chemical bonding method, a water jet method, a needle punch method, and a stitch bonding method.
- filament opening and webbing After blending a plurality of kinds of fibers, filament opening and webbing are performed with a carding device, and then this obtained web is treated by a nonwoven fabric manufacturing installation to produce the nonwoven fabric.
- Manufacturing by a needle punching system is preferable from a viewpoint of simplicity of apparatus, and manufacturing by a thermofusible adhesion system is preferable when low melting point polyester based binder fiber.
- the flame resistant fiber composite of the present invention may include antistatic agents, agents for prevention of coloring by heat, light resistance improvers, whiteness improvers, matting inhibitors, etc., and moreover coloring and dyeing by means of dyestuffs, pigments, etc. may be given without any trouble.
- flame resistant fiber composite of the present invention has desired flame resistance, and demonstrates characteristics excellent in touch, feeling, moisture absorptivity, sensuousness, etc.
- Upholstered furniture of the present invention are beddings, such as bed mattress, chairs, sofas, and seats for vehicles etc. covered by the previously described flame resistant fiber composite.
- bed mattress for example, a pocket coil mattress, a box coil mattress using metal coils inside, or mattresses using insulators, such as styrene and urethane resins of a foamed state inside may be mentioned. Since demonstration of flame retardation by means of the flame resistant composite used for the present invention enables prevention of spread of a fire to a structure inside the mattress, mattresses having excellent flame resistance and simultaneously outstanding touch, or feeling may be obtained in any structures.
- chairs there may be mentioned chairs used indoors, such as stools, bench, side chairs, armchairs, lounge chair sofas, seat unit (sectional chairs, separated chairs), locking chairs, folding chairs, stacking chairs, swivel chairs, or seats used outdoors for seating for vehicles etc., such as, automobile seat, seat for vessels, seat for airplanes, seat for trains etc. Also in these chairs, upholstered products having functions to prevent internal spread of a fire, and simultaneously having visual appearance and feeling needed for usual furniture may be obtained.
- mattresses and chairs using low repulsion urethane foams represented by Tempur material (manufactured by Tempur World, Inc.) and having pressure dispersion function is extremely flammable as compared to mattresses and chairs using foamed material of usual styrene and urethane resins.
- demonstration of flame retardation by means of the flame resistant fiber composite used for the present invention can prevent spread of a fire to the low repulsion urethane foam as an internal structure of the mattresses or chairs.
- Examples of usage of the flame resistant fiber composite of the present invention to upholstered furniture products include use in a form of textile fabrics or knittings on a surface cloth, and interposition in a form of textile fabrics, or knittings and nonwoven fabrics between a surface cloth and internal structure, for example, urethane foams and packing.
- a conventional cloth may only be replaced with a cloth comprising the flame resistant fiber composite of the present invention.
- a nonwoven fabric comprising the flame resistant fiber composite of the present invention covers the whole internal structure, or at least in a portion contacting a surface cloth a nonwoven fabric comprising the flame resistant fiber composite of the present invention is certainly disposed on an outside surface of the internal structure, and subsequently a surface cloth is disposed outside thereon.
- upholstered furniture products having highly excellent flame resistance as outstanding characteristics of the flame resistant fiber composite of the present invention, and having characteristics excellent also in touch, feeling, moisture absorptivity, sensuousness, etc.
- a fiber prepared according to the following Manufacturing Examples 2 g was sampled, and the fiber was equally divided into 8 samples to obtain 8 twisted fiber bundles with a length of approximately 6 cm.
- the samples were vertically fixed to a holder of an oxygen index measuring instrument made by SUGA TEST INSTRUMENT Co., LTD. (ON-1 type). Lowest oxygen concentration necessary for the 5 cm of samples to continue burning was measured to obtain an LOI value. Larger LOI value means that it is difficult for the sample to burn with higher flame resistance.
- Fibers prepared according to following Manufacturing Examples were opened with a roller carding device, and subsequently, nonwoven fabrics having weight of 300 g/m 2 and measuring 20 cm x 20 cm were prepared by a needle punch method.
- a perlite board with sides of 200 mm by 200 mm, and a thickness of 10 mm having a hole with a diameter of 15cm in a center thereof was prepared.
- a nonwoven fabric for flame resistance evaluation examination was disposed on the board, and four sides of the nonwoven fabric were fixed with clips so that the nonwoven fabric for flame resistance evaluation examination might not shrink at the time of heating.
- the sample was set so that a center of the sample might meet a center of a burner and that a surface of the nonwoven fabric for flame resistance evaluation examination might show upwards, in a position separated from the burner face by 40 mm to a gas stove (made by Paloma LTD, PA-10H-2).
- a gas stove made by Paloma LTD, PA-10H-2
- propane having a purity of not less than 99% was used, and a contact period to flame was set as 180 seconds, and a height of the flame as 25 mm.
- Evaluation B was a case where a carbonized layer of the nonwoven fabric for flame resistance evaluation examination had no perforated holes and no cracks, and a case where it had both of holes and cracks was evaluated as C. Evaluation B was determined as passed.
- a fiber prepared according to the following Manufacturing Examples 2 g was sampled, the fiber was equally divided into 8 samples to obtain 8 twisted fiber bundles with a length of approximately 6 cm.
- a mending tape (Sumitomo 3M Limited, Scotch mending tape) was attached twice around an end of the twisted fiber bundle so that a width of 13 mm might be given, and subsequently, while maintained horizontally, an end of the twisted fiber bundle was contacted with a flame for 2 seconds. The sample was kept standing to maintain the state, and a period (fire extinguishing period) until the fire was extinguished was measured.
- a shorter fire extinguishing period means a higher flame resistance that is a higher self-extinguishing effect.
- thermo-gravimetry made by Seiko Instruments, TG/DTA220, gas used: air, amount of gas flow: 200 ml/min, heating rate: 3 degrees C/min).
- An initial weight was set as 100% and a weight of a residual matter (carbide) at 500 degrees C was represented with a ratio.
- a larger number preferably represents a larger amount of residual matter (carbide).
- This spinning solution was extruded into a 50% dimethylformamide aqueous solution using a nozzle having 0.10 mm of a nozzle hole diameter and a number of holes of 1000 holes, and the fiber obtained was dried at 120 degrees C after washing. Subsequently, after stretching by 3 times, the fiber was heat-treated for 5 minutes at 150 degrees C, and furthermore the fiber was cut to obtain a halogen containing fiber. Obtained fiber was a staple fiber having a size of a fiber of 5.6 dtex, and a 51 mm cut length.
- a copolymer consisting of acrylonitrile 49%, vinyl chloride 50.5%, and p-sodium styrene sulfonate 0.5% was dissolved in dimethylformamide to obtain a resin solution having a resin concentration of 30%.
- zinc oxide three kinds of zinc oxides manufactured by Sakai Chemical Ind. Co. Ltd.
- antimony trioxide as an antimony compound
- kaolin kaolin ASP 170 manufactured by Engelhard Corporation
- the spinning solutions were extruded into a 50% dimethylformamide aqueous solution using a nozzle having 0.10 mm of a nozzle hole diameter and a number of holes of 1000 holes, the fibers obtained were dried at 120 degrees C after washing. Subsequently, after stretching by 3 times, the fibers were heat-treated for 5 minutes at 130 degrees C, and furthermore the fiber was cut to obtain halogen containing fibers. Obtained fibers were staple fibers having a size of a fiber of 5.6 dtex, and a 51 mm cut length.
- halogen containing fibers including zinc oxide as a zinc compound, antimony trioxide as an antimony compound, and kaolin as an inorganic compound in amounts in Table 1 were produced.
- Example 4 also had advanced flame resistance, and Example 3 included equivalent amount of zinc oxide and of kaolin as in Example 4 and, Example 3 included antimony trioxide, and therefore had a shorter twisted fiber bundle fire extinguishing period, exhibiting more advanced flame resistance.
- Comparative Example 1 had an equivalent amount of antimony trioxide and a total amount of additives as in Example 1, it did not include kaolin, and therefore Comparative Example 1 failed to form satisfactory carbonized layer but makes nonwoven fabric cause perforation, and furthermore demonstrated a low LOI value and low residual ratio at the time of heating, and gave comprehensive judgment of failure.
- Comparative Example 2 had an equivalent amount of antimony trioxide and a total amount of additives as in Example 1, it did not include zinc oxide, and therefore Comparative Example 2 failed to form satisfactory carbonized layer but made nonwoven fabric cause perforation, and furthermore demonstrated a low LOI value and gave comprehensive judgment of failure.
- Comparative Example 3 had a small total amount of zinc oxide and kaolin, made nonwoven fabric cause perforation, without forming satisfactory carbonized layer, Comparative Example 3 was not judged to have advanced flame resistance, but comprehensive judgment gave failure.
- Table 1 shows flame resistance evaluation test results of Examples 1 to 4 and Comparative Examples 1 to 3.
- Table 1 Amount of additives (parts by weight) Flame resistance evaluation result Residual ratio at the time of heating (%) Comprehensive evaluation Zinc oxide Antimony trioxide Kaolin Additives total amount LOI value Nonwoven fabric Twisted fiber bundle fire extinguishing period(sec) Ex.
- halogen containing fibers comprising zinc oxide as zinc compound, antimony trioxide as antimony compound, and aluminum hydroxide as other inorganic compound as shown in Table 2.
- LOI values, flame resistance evaluation in nonwoven fabric, and residual ratio measurement at the time of combustion by means of thermogravimetric measurement were measured for the obtained fibers. Table 2 shows results.
- Examples 5 to 9 gave satisfactory combustion test results. They gave high LOI values, in nonwoven fabric examination, they sufficiently formed satisfactory carbonized layer and generated neither perforations nor cracks after heating by means of gas stove. Furthermore, they demonstrated high residual ratios at the time of heating and therefore they were judged to have advanced flame resistance, giving satisfactory comprehensive judgment.
- Example 8 also had advanced flame resistance, and since Example 7 had equivalent amount of zinc oxide and aluminum hydroxide as in Example 8, and included antimony trioxide, it showed a shorter twisted fiber bundle fire extinguishing period, and had more advanced flame resistance.
- Comparative Example 4 had an equivalent amount of antimony trioxide, and total amount of additives as in Example 5, but did not have zinc oxide, and it made a nonwoven fabric cause perforation, without formation of satisfactory carbonized layer. Comparative Example 4 had low residual ratio at the time of combustion. It gave comprehensive judgment of failure.
- Comparative Example 5 Since Comparative Example 5 had a small amount of total of zinc oxide and aluminum hydroxide, it made nonwoven fabric to cause perforation, without forming satisfactory carbonized layer. It was not judged to have advanced flame resistance, giving comprehensive judgment of failure.
- Table 2 shows flame resistance evaluation test results of Examples 5 to 9 and Comparative Examples 4 and 5. Table 2 Amount of additives (parts by weight) Flame resistance evaluation result Residual ratio at the time of heating (%) Comprehensive evaluation Zinc oxide Antimony trioxide Alumi num hydroxide Additives total amount LOI value Nonwoven fabric Twisted fiber bundle fire extinguishing period(sec) Ex.
- halogen containing fibers comprising zinc oxide as zinc compound, antimony trioxide as antimony compound, and kaolin as other inorganic compound as shown in Table 3.
- LOI values, flame resistance evaluation in nonwoven fabric, and residual ratio measurement at the time of combustion by means of thermogravimetric measurement were measured for the obtained fibers. Table 3 shows results.
- Examples 10 and 11 gave satisfactory combustion test results. They gave high LOI values, in nonwoven fabric examination, they formed satisfactory carbonized layer and generated neither perforations nor cracks after heating by means of gas stove. Furthermore, they demonstrated high residual ratios at the time of heating and therefore they were judged to have advanced flame resistance, giving satisfactory comprehensive judgment.
- Comparative Example 6 had an equivalent amount of antimony trioxide and kaolin as in Examples 10 and 11, it did not have zinc oxide, and therefore, it formed perforation in a nonwoven fabric without forming satisfactory carbonized layer. And furthermore, since it had a low residual ratio at the time of heating, it gave comprehensive judgment of failure.
- Table 3 shows flame resistance evaluation test results of Examples 10 and 11 and Comparative Example 6. Table 3 Amount of additives (parts by weight) Flame resistance evaluation result Residual ratio at the time of heating (%) Comprehensive evaluation Zinc oxide Antimony trioxide Kaolin Additives total amount LOI value Nonwoven fabric Twisted fiber bundle fire extinguishing period(sec) Ex. 10 10 10 20 45 39 B 18 67 Passed 11 5 10 20 35 40 B 19 63 Passed Com. Ex. 6 0 10 20 30 41 C 18 50 Failed
- halogen containing fibers comprising zinc oxide as zinc compound, antimony trioxide as antimony compound, and aluminum hydroxide as other inorganic compound as shown in Table 4.
- LOI values, flame resistance evaluation in nonwoven fabric, and residual ratio measurement at the time of combustion by means of thermogravimetric measurement were measured for the obtained fibers. Table 4 shows results.
- Examples 12 and 13 gave satisfactory combustion test results. They gave high LOI values, in nonwoven fabric examination, they formed satisfactory carbonized layer and generate neither perforations nor cracks after heating by means of gas stove. Furthermore, they demonstrated high residual ratios at the time of heating and therefore they were judged to have advanced flame resistance, giving satisfactory comprehensive judgment.
- Comparative Example 7 had an equivalent amount of antimony trioxide and aluminum hydroxide as in Examples 12 and 13, it did not have zinc oxide, and therefore it formed perforation in a nonwoven fabric without forming satisfactory carbonized layer. And furthermore, since it had a low residual ratio at the time of heating, it gave comprehensive judgment of failure.
- Table 4 shows flame resistance evaluation test results of Examples 12 and 13 and Comparative Example 7.
- Table 4 Amount of additives (parts by weight) Flame resistance evaluation result Residual ratio at the time of heating (%) Comprehensive evaluation Zinc oxide Antimony trioxide Aluminum hydroxide Additives total amount LOI value Nonwoven fabric Twisted fiber bundle fire extinguishing period(sec) Ex. 12 15 10 20 45 45 B 10 70 Passed 13 5 10 20 35 47 B 9 66 Passed Com. Ex. 7 0 10 20 30 48 C 11 52 Failed
- These evaluation methods are simple evaluation methods for a case wherein firing of flame to the internal structure in the case where fire is prevented by inserting a flame resistant nonwoven fabric of the present invention between a surface fabrics for upholstered furniture, such as bed mattresses, chairs, or sofas, and an internal structure such as urethane foam or packing etc.
- a fiber mixed at a predetermined ratio was opened with a carding device, subsequently, using a needle punch method obtained was a nonwoven fabric with a weight of 200 g/m 2 , and a width of 20 cm and a length of 20 cm for flame resistance evaluation examination.
- a perlite board with sides of 200 mm by 200 mm, and a thickness of 10 mm having a hole with a diameter of 15 cm in a center thereof was prepared.
- a nonwoven fabric for flame resistance evaluation examination was disposed on the board, and four sides of the nonwoven fabric were fixed with clips so that the nonwoven fabric for flame resistance evaluation examination might not shrink at the time of heating.
- the sample nonwoven fabric was set so that a center of the sample might meet a center of a burner and that a surface of the nonwoven fabric for flame resistance evaluation examination might show upwards, in a position separated from the burner face by 40 mm to a gas stove (made by Paloma LTD, PA-10H-2).
- a gas stove made by Paloma LTD, PA-10H-2
- propane having a purity of not less than 99% was used, and a contact period to flame was set as 180 seconds, and a height of the flame as 25 mm.
- a fiber mixed at a predetermined ratio was opened with a carding device, and subsequently, using a needle punch method obtained was a nonwoven fabric with a weight of 200 g/m 2 , and a width of 30 cm and a length of 45 cm.
- Beneath the nonwoven fabric a urethane foam (length of 45 cm, width of 30 cm and thickness of 53 mm) was disposed in layers, a polyester nonwoven fabric (weight 300 g/m 2 ) having a same size, and furthermore a fabric made of polyester (unit weight 120 g/m 2 ) were disposed on the nonwoven fabric in layers. These four layers were fixed with stapler so that they might not shift, to give a sample for flame resistance evaluation examination.
- A was a case where card processability at the time of carding of nonwoven fabric (easiness of processing) was satisfactory, B a case where card processing was possible, and C a case where card processing was difficult due to occurrence of waste fibers.
- a and B were evaluated as passed.
- a resin weight of the obtained resin solution added were zinc oxide (three kinds of zinc oxides manufactured by Sakai Chemical Ind., Co., Ltd.) as zinc compounds; antimony trioxide as an antimony compound; and kaolin (kaolin ASP170 manufactured by Engelhard Corporation) as an other inorganic compound or aluminum hydroxide, as shown in Tables 1, 2, 5, and 6 to obtain spinning solutions.
- This spinning solutions were extruded into a 50% dimethylformamide aqueous solution using a nozzle having 0.10 mm of a nozzle hole diameter and a number of holes of 1000 holes to be coagulated, and the fibers obtained were dried at 120 degrees C after washing. Subsequently, after stretching by 3 times, the fibers were heat-treated for 5 minutes at 150 degrees C, and furthermore the fibers were cut to obtain a halogen containing fibers. Obtained fibers were staple fibers having a size of a fiber of 5. 6 dtex, and a 51 mm cut length.
- a copolymer consisting of acrylonitrile 49%, vinyl chloride 50.5%, and p-sodium styrene sulfonate 0.5% (Halogen atom ratio: 34%) was dissolved in dimethylformamide to obtain a resin solution having a resin concentration of 30%.
- To a resin weight of the obtained resin solution added were zinc oxide (three kinds of zinc oxides manufactured by Sakai Chemical Ind., Co., Ltd.) as zinc compounds; antimony trioxide as an antimony compound; and kaolin (kaolin ASP] 70 manufactured by Engelhard Corporation) as an other inorganic compound or aluminum hydroxide, as shown in Tables 3 and 4 to obtain spinning solutions.
- the spinning solutions were extruded into a 50% dimethylformamide aqueous solution using a nozzle having 0.10 mm of a nozzle hole diameter and a number of holes of 1000 holes, and the fibers obtained were dried at 120 degrees C after washing. Subsequently, after stretching by 3 times, the fibers were heat-treated for 5 minutes at 130 degrees C, and furthermore the fibers were cut to obtain halogen containing fibers. Obtained fibers were staple fibers having a size of a fiber of 5.6 dtex, and a 51 mm cut length.
- halogen containing fibers including zinc oxide as a zinc compound, antimony trioxide as an antimony compound, and kaolin as an inorganic compound in amounts in Table 5 were produced. Then nonwoven fabrics consisting of predetermined ratios of the obtained halogen containing fibers, a polyester fiber (6. 6 dtex, 51 mm of cut length), and a rayon fiber (1.5 dtex, 38 mm of cut length) were prepared for flame resistance evaluation test 1. Table 5 shows results.
- Comparative Examples 8 to 9 had an equivalent amount of flame resistant agent as in Example 14, but since Comparative Example 8 did not include kaolin as an other inorganic compound, and Comparative Example 9 did not include zinc oxide as zinc compound, they could not form satisfactory carbonized film but gave occurrence of perforations therein.
- Comparative Example 11 included a small quantity of halogen containing fiber, and failed to form satisfactory carbonized film.
- Comparative Example 11 demonstrated satisfactory flame resistance based on 100% of content of the halogen containing fiber, but since it did not include any natural fibers and/or chemical fibers, it gave a problem in processability at the time of nonwoven fabric preparation.
- Table 5 shows flame resistance evaluation test results of Examples 14 to 19 and Comparative Examples 8 to 11.
- Table 5 Amount of addition in halogen containing fiber (parts by weight) Ratio of fibers constituting nonwoven fabric (parts by weight) Flame resistance evaluation result Processability evaluation Comprehensive evaluation Zinc oxide Antimony trioxide Kaolin Additive total amount Halogen containing fiber Rayon fiber Polyester fiber State of nonwoven fabric Ex.
- halogen containing fibers comprising zinc oxide as zinc compound, antimony trioxide as antimony compound, and aluminum hydroxide as other inorganic compound as shown in Table 6. Then nonwoven fabrics consisting of predetermined ratios of the obtained halogen containing fibers, a polyester fiber (6. 6 dtex, 51 mm of cut length), and a rayon fiber (1. 5 dtex, 38 mm of cut length), and cotton were prepared for flame resistance evaluation test 2. Table 6 shows evaluation results.
- Examples 20 to 27 gave satisfactory combustion test results.
- the nonwoven fabrics for flame resistance evaluation examination did not give occurrence of any cracks or perforations, but formed satisfactory carbonized films.
- Comparative Examples 12 to 14 included equivalent amounts of flame resistant agents as in Example 14, Comparative Example 12 could not form satisfactory carbonized films, and gave perforations in the nonwoven fabrics due to absence of zinc oxide as zinc compound therein.
- Comparative Example 13 had a small amount of content of the halogen containing fiber, and could not form satisfactory carbonized film.
- Comparative Example 14 demonstrated satisfactory flame resistance based on 100% of content of the halogen containing fiber, but since it did not include any natural fibers and/or chemical fibers, it gave a problem in processability at the time of nonwoven fabric preparation.
- Table 6 shows flame resistance evaluation test results of Examples 20 to 27 and Comparative Examples 12 to 14. Table 6 Amount of addition in halogen containing fiber (parts by weight) Ratio of fibers constituting nonwoven fabric (parts by weight) Flame resistance evaluation result Processability evaluati on Comprehensive evaluation Zinc oxyde Antimony trioxide Aluminum hydroxide Additive total amount Halogen containing fiber Rayon fiber Cotton fiber Polyester fiber State of nonwoven fabric Ex.
- halogen containing fibers including zinc oxide as a zinc compound, antimony trioxide as an antimony compound, and kaolin as an inorganic compound in amounts in Table 7 were produced. Then nonwoven fabrics consisting of predetermined ratios of the obtained halogen containing fibers, a polyester fiber (6. 6 dtex, 51 mm of cut length), and a rayon fiber (1.5 dtex, 38 mm of cut length) were prepared for flame resistance evaluation test 2. Table 7 shows evaluation results.
- Examples 28 to 30 gave satisfactory combustion test results.
- the nonwoven fabrics for flame resistance evaluation examination did not give occurrence of any cracks or perforations, but formed satisfactory carbonized films after heating by means of gas stove.
- Comparative Example 15 included equivalent amounts of antimony compounds, and kaolin as in Examples 28 to 30, but it could not form a satisfactory carbonized film but gave perforations caused in the nonwoven fabric due to the absence of zinc oxide as zinc compound.
- Table 7 shows flame resistance evaluation test results of
- halogen containing fibers comprising zinc oxide as zinc compound, antimony trioxide as antimony compound, and aluminum hydroxide as other inorganic compound as shown in Table 8. Then nonwoven fabrics consisting of predetermined ratios of the obtained halogen containing fibers, a polyester fiber (6. 6 dtex, 51 mm of cut length), and a rayon fiber (1.5 dtex, 38 mm of cut length) were prepared for flame resistance evaluation test 2. Table 8 shows results.
- Examples 31 to 33 gave satisfactory combustion test results, nonwoven fabrics for flame resistance evaluation examination gave occurrence of neither cracks nor perforations after heating by means of a gas stove, but formed satisfactory carbonized film.
- Comparative Example 16 included equivalent amounts of antimony trioxide and aluminum hydroxide as in Examples 31 to 33, but it could not form a satisfactory carbonized film but gave perforations caused in the nonwoven fabric due to the absence of zinc oxide as zinc compound.
- Table 8 shows flame resistance evaluation test results of Examples 31 to 33 and Comparative Example 16. Table 8 Amount of addition in halogen containing fiber (parts by weight) Ratio of fibers consituting nonwoven fabric (parts by weight) Flame resistance evaluation result Processability evaluation Comprehensive evaluation Zinc oxide Antimony trioxide Aluminum hyd roxide Additive total amount Halogen containing fiber Rayon fiber Polyester fiber State of nonwoven fabric Ex. 31 15 10 20 45 40 40 20 A A Passed 32 15 10 20 45 20 60 20 A A Passed 33 15 10 20 45 20 40 40 A A Passed Com. Ex. 16 0 10 20 30 40 40 20 C B Failed
- halogen containing fibers including zinc oxide as a zinc compound, antimony trioxide as an antimony compound, and kaolin as an inorganic compound in amounts in Table 9 were produced. Then nonwoven fabrics consisting of predetermined ratios of the obtained halogen containing fibers, a polyester fiber (6. 6 dtex, 51 mm of cut length), and a rayon fiber (1.5 dtex, 38 mm of cut length) were prepared for flame resistance evaluation test 3. Table 9 shows results.
- Examples 34 to 36 gave satisfactory combustion test results, and formed satisfactory carbonized films, and flaming to urethane foam was not observed.
- Comparative Example 17 included an equivalent amount of an antimony compound and kaolin as in Examples 34 to 36, but since it did not include zinc oxide as a zinc compound, it could not form satisfactory carbonized film but gave flaming to urethane foam.
- Table 9 shows flame resistance evaluation test results of Examples 34 to 36 and Comparative Example 17. Table 9 Amount of addition in halogen containing fiber (parts by weight) Ratio of fibers consituting nonwoven fabric (parts by weight) Flame resistance evaluation result Zinc oxide Antimony trioxide Kaolin Additive total amount Halogen containing fiber Rayon fiber Polyester fiber Ex. 34 15 10 20 45 40 40 20 A 35 5 10 20 35 40 40 20 B 36 10 5 20 35 40 40 20 A Com. Ex. 17 0 10 20 30 40 40 20 C
- halogen containing fibers including zinc oxide as a zinc compound, antimony trioxide as an antimony compound, and kaolin as an inorganic compound in amounts in Table 9 were produced. Then nonwoven fabrics consisting of predetermined ratios of the obtained halogen containing fibers, a polyester fiber (6. 6 dtex, 51 mm of cut length), and a rayon fiber (1.5 dtex, 38 mm of cut length) were prepared for flame resistance evaluation test 3. Table 10 shows results.
- Examples 37 to 39 gave satisfactory combustion test results, and formed satisfactory carbonized films, and flaming to urethane foam was not observed.
- Comparative Example 18 included an equivalent amount of an antimony compound and kaolin as in Examples 37 to 38, but since it did not include zinc oxide as a zinc compound, it could not form satisfactory carbonized film but gave flaming to urethane foam.
- Table 10 shows flame resistance evaluation test results of Examples 37 to 39 and Comparative Example 18 Table 10 Amount of addition in halogen containing fiber (parts by weight) Ratio of fibers consituting nonwoven fabric (parts by weight) Flame resistance evaluation result Zinc oxide Antimony trioxide Aluminum hydroxide Additive total amount Halogen containing fiber Rayon fiber Polyester fiber Ex. 37 15 10 20 45 40 40 20 A 38 5 10 20 35 40 40 20 A 39 10 5 20 35 40 40 20 B Com. Ex. 18 0 10 20 30 40 40 20 C
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Preliminary Treatment Of Fibers (AREA)
Claims (14)
- Eine flammhemmende synthetische Faser, umfassend:100 Gewichtsteile eines Polymers, welches nicht weniger als 17 Gew.-% an Halogenatomen enthält;3 bis 50 Gewichtsteile einer Zinkverbindung, ausgewählt aus Zink, Zinkoxid und Zinkcarbonat;0 bis 30 Gewichtsteile einer Antimonverbindung; und3 bis 30 Gewichtsteile einer anderen anorganischen Verbindung, ausgewählt aus natürlichen oder synthetischen Verbindungen auf Mineralbasis, Verbindungen auf Aluminiumbasis, Magnesiumverbindungen und Siliciumverbindungen,
wobei die Gesamtmenge der Zinkverbindung, der Antimonverbindung und der anderen anorganischen Verbindung nicht weniger als 15 Gewichtsteile beträgt. - Die flammhemmende synthetische Faser gemäß Anspruch 1, wobei das Polymer, welches weniger als 17 Gew.-% an Halogenatomen enthält, aus30 bis 70 Gewichtsteilen Acrylonitril;70 bis 30 Gewichtsteilen Halogen enthaltendem Vinyl- und/oder Halogen enthaltendem Vinylidenmonomer; und0 bis 10 Gewichtsteilen eines Vinylmonomers, das mit den Monomeren copolymerisierbar ist, besteht.
- Die flammhemmende synthetische Faser gemäß Anspruch 1, wobei:die natürliche oder synthetische Verbindung auf Mineralbasis ausgewählt ist aus Kaolin, Zeolith, Montmorillonit, Talk, Perlit, Bentonit, Vermiculit, Diatomeenerde und Graphit; die Verbindung auf Aluminiumbasis ausgewählt ist aus Aluminiumhydroxid, Aluminiumsulfat und Aluminiumsilicat;die Magnesiumverbindung ausgewählt ist aus Magnesiumhydroxid und Magnesiumoxid;
oderdie Siliciumverbindung ausgewählt ist aus Silicat und Gläsern. - Die flammhemmende synthetische Faser gemäß Anspruch 1, umfassend:100 Gewichtsteile des Polymers, welches nicht weniger als 17 Gew.-% an Halogenatomen enthält;3 bis 30 Gewichtsteile der Zinkverbindung;0 bis 30 Gewichtsteile der Antimonverbindung; und3 bis 30 Gewichtsteile Kaolin oder Aluminiumhydroxid als die andere anorganische Verbindung,
wobei die Gesamtmenge der Zinkverbindung, der Antimonverbindung und der anderen anorganischen Verbindung 20 bis 50 Gewichtsteile beträgt. - Ein flammhemmender Faserkomposit, bestehend aus:nicht weniger als 10 Gewichtsteilen einer Faser (A) undnicht mehr als 90 Gewichtsteilen einer natürlichen Faser und/oder einer chemischen Faser (B),
wobei die Faser (A) umfasst:100 Gewichtsteile eines Polymers, welches nicht weniger als 17 Gew.-% an Halogenatomen enthält;3 bis 50 Gewichtsteile einer Zinkverbindung, ausgewählt aus Zink, Zinkoxid und Zinkcarbonat;0 bis 30 Gewichtsteile einer Antimonverbindung; und3 bis 30 Gewichtsteile einer anderen anorganischen Verbindung, ausgewählt aus natürlichen oder synthetischen Verbindungen auf Mineralbasis, Verbindungen auf Aluminiumbasis, Magnesiumverbindungen und Siliciumverbindungen, und
wobei die Gesamtmenge der Zinkverbindung, der Antimonverbindung und der anderen anorganischen Verbindung nicht weniger als 15 Gewichtsteile beträgt. - Der flammhemmende Faserkomposit gemäß Anspruch 5, wobei das Polymer, welches nicht weniger als 17 Gew.-% an Halogenatomen enthält, ein Copolymer ist, umfassend: 30 bis 70 Gewichtsteile Acrylonitril;70 bis 30 Gewichtsteile eines Halogen enthaltenden Vinyl- und/oder Halogen enthaltenden Vinylidenmonomers; und0 bis 10 Gewichtsteile eines damit copolymerisierbaren Vinylmonomers.
- Der flammhemmende Faserkomposit gemäß Anspruch 5 oder 6, wobei:die natürliche oder synthetische Verbindung auf Mineralbasis ausgewählt ist aus Kaolin, Zeolith, Montmorillonit, Talk, Perlit, Bentonit, Vermiculit, Diatomeenerde und Graphit;die Verbindung auf Aluminiumbasis ausgewählt ist aus Aluminiumhydroxid, Aluminiumsulfat und Aluminiumsilicat;die Magnesiumverbindung ausgewählt ist aus Magnesiumhydroxid und Magnesiumoxid;
oderdie Siliciumverbindung ausgewählt ist aus Silicat und Gläsern. - Der flammhemmende Faserkomposit gemäß Anspruch 7, wobei die chemische Faser der mindestens einen Faserart in der natürlichen Faser und/oder chemischen Faser (B) eine Polyesterfaser ist und die Menge der Polyesterfaser nicht mehr als 40 Gewichtsteile beträgt.
- Der flammhemmende Faserkomposit gemäß Anspruch 8, wobei die Polyesterfaser eine Bindemittelfaser mit niedrigem Schmelzpunkt ist.
- Ein Vliesstoff, umfassend den flammhemmenden Faserkomposit gemäß einem der Ansprüche 5 bis 9.
- Eine Flammschutzbarriere, umfassend den Vliesstoff gemäß Anspruch 10.
- Ein Polstermöbelgegenstand, umfassend den flammhemmenden Faserkomposit gemäß einem der Ansprüche 5 bis 9.
- Ein Polstermöbelgegenstand, umfassend den Vliesstoff gemäß Anspruch 10.
- Ein Polstermöbelgegenstand, umfassend die Flammschutzbarriere gemäß Anspruch 11.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004296443 | 2004-10-08 | ||
JP2004299406 | 2004-10-13 | ||
PCT/JP2005/014692 WO2006040873A1 (ja) | 2004-10-08 | 2005-08-10 | 難燃性合成繊維、難燃繊維複合体及びそれを用いた布張り家具製品 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1798318A1 EP1798318A1 (de) | 2007-06-20 |
EP1798318A4 EP1798318A4 (de) | 2008-07-30 |
EP1798318B1 true EP1798318B1 (de) | 2010-10-27 |
Family
ID=36148175
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05770521A Active EP1798318B1 (de) | 2004-10-08 | 2005-08-10 | Flammhemmende synthetische faser, flammhemmender faserkomposit sowie damit hergestelltes polstermöbel |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1798318B1 (de) |
JP (1) | JPWO2006040873A1 (de) |
AT (1) | ATE486160T1 (de) |
DE (1) | DE602005024423D1 (de) |
WO (1) | WO2006040873A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009093562A1 (ja) * | 2008-01-21 | 2009-07-30 | Kaneka Corporation | 難燃性繊維、難燃性繊維シート及びそれらの製造方法 |
EP2488683B1 (de) | 2009-10-13 | 2018-08-29 | Lenzing Aktiengesellschaft | Feuerbarrieren umfassend feuerfeste lyocell-fasern |
EP2563958A4 (de) | 2010-04-30 | 2017-03-15 | Drifire, LLC | Fasergemische für kleidungsstücke mit guten wärme-, abreibungsfestigkeits- und feuchtigkeitsmanagement-eigenschaften |
EP2896634B1 (de) * | 2014-01-16 | 2016-05-04 | Formosa Plastics Corporation | Verfahren zur Herstellung eines flammhemmenden Copolymer auf Basis eines modifizierten Acrylonitrils und eines flammhemmenden Fasermaterials |
CN105113286A (zh) * | 2015-07-28 | 2015-12-02 | 太仓市宝明化纤有限公司 | 一种高固色高阻燃的涤纶织物的染整工艺 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5436702B2 (de) * | 1972-10-18 | 1979-11-10 | ||
JPS526371B2 (de) * | 1973-07-06 | 1977-02-22 | ||
US3983290A (en) * | 1974-09-03 | 1976-09-28 | Stauffer Chemical Company | Fire retardant polyvinyl chloride containing compositions |
US3985706A (en) * | 1975-03-24 | 1976-10-12 | The Firestone Tire & Rubber Company | Smoke-retardant for chlorinated polyethylene and vinyl chloride polymers |
JPS5930803B2 (ja) * | 1976-08-24 | 1984-07-28 | 鐘淵化学工業株式会社 | 難燃性に優れたアクリル系合成繊維 |
JPS6189339A (ja) * | 1984-10-05 | 1986-05-07 | 鐘淵化学工業株式会社 | 複合難燃繊維 |
US5342874A (en) * | 1989-07-21 | 1994-08-30 | Alcan International Limited | Flame retardant polymer formulation |
JP3004107B2 (ja) * | 1991-11-26 | 2000-01-31 | 鐘淵化学工業株式会社 | 難燃繊維複合体 |
JP3525237B2 (ja) * | 1996-06-12 | 2004-05-10 | 鐘淵化学工業株式会社 | ハロゲン含有繊維を用いた難燃繊維複合体 |
CN1259472C (zh) * | 1999-11-04 | 2006-06-14 | 钟渊化学工业株式会社 | 难燃性交织织物 |
JP3797170B2 (ja) * | 2001-09-25 | 2006-07-12 | 株式会社カネカ | アクリル系合成繊維及びその繊維複合体 |
-
2005
- 2005-08-10 DE DE602005024423T patent/DE602005024423D1/de active Active
- 2005-08-10 AT AT05770521T patent/ATE486160T1/de not_active IP Right Cessation
- 2005-08-10 JP JP2006540842A patent/JPWO2006040873A1/ja not_active Withdrawn
- 2005-08-10 WO PCT/JP2005/014692 patent/WO2006040873A1/ja active Application Filing
- 2005-08-10 EP EP05770521A patent/EP1798318B1/de active Active
Also Published As
Publication number | Publication date |
---|---|
EP1798318A1 (de) | 2007-06-20 |
WO2006040873A1 (ja) | 2006-04-20 |
EP1798318A4 (de) | 2008-07-30 |
ATE486160T1 (de) | 2010-11-15 |
DE602005024423D1 (de) | 2010-12-09 |
JPWO2006040873A1 (ja) | 2008-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI408266B (zh) | 難燃性合成纖維與難燃纖維集合體及該等之製造方法、與纖維製品 | |
EP1619278B1 (de) | Flammfester faserverbund sowie daraus hergestelltes textiles flächengebilde | |
EP1743962B1 (de) | Flammenhemmende synthetische faser und unter verwendung derselben hergestellte flammenhemmende textilwaren. | |
US20050118919A1 (en) | Flame blocking liner materials | |
TWI530597B (zh) | A flame retardant fiber aggregate and a method for manufacturing the same, and a fiber product | |
EP1798318B1 (de) | Flammhemmende synthetische faser, flammhemmender faserkomposit sowie damit hergestelltes polstermöbel | |
US20220167700A1 (en) | Flame-retardant fiber composite and flame-retardant working clothes | |
US20070237953A1 (en) | Flame resistant synthetic fiber, flame resistant fiber composite and upholstered furniture products using the same | |
JP2007291570A (ja) | 難燃性合成繊維、難燃繊維複合体およびそれを用いた炎遮断性バリア用不織布 | |
JP4346566B2 (ja) | 難燃性合成繊維および該難燃性合成繊維を用いた難燃性繊維複合体および該難燃性繊維複合体を用いた布張り家具製品 | |
WO2022181337A1 (ja) | 難燃性アクリル系繊維、難燃性繊維複合体、及び難燃性マットレス | |
WO2010010639A1 (ja) | 難燃性合成繊維とその製造方法、難燃繊維複合体及び繊維製品 | |
JP2007291571A (ja) | 難燃性合成繊維、難燃繊維複合体およびそれを用いた難燃性マットレス | |
JP4777892B2 (ja) | 難燃性合成繊維、難燃繊維複合体およびそれを用いた布張り家具製品 | |
WO2023100484A1 (ja) | 難燃性布帛、及びそれを含む難燃性マットレス | |
JP2009242957A (ja) | 難燃性合成繊維、それを用いた炎遮蔽性生地及び難燃性布張り製品 | |
JP2007270411A (ja) | 難燃性合成繊維、難燃繊維複合体およびそれを用いた布張り家具製品 | |
JPWO2006008958A1 (ja) | 難燃性合成繊維、難燃繊維複合体および難燃繊維複合体を用いた布張り家具製品 | |
JP2007308849A (ja) | 難燃性合成繊維、難燃繊維複合体およびそれを用いた布張り家具製品 | |
JP2007169794A (ja) | 難燃性合成繊維、難燃繊維複合体及びそれを用いた布張り家具製品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20070426 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20080627 |
|
17Q | First examination report despatched |
Effective date: 20081202 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602005024423 Country of ref document: DE Date of ref document: 20101209 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20101027 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20101027 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20101027 |
|
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: 20101027 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: 20101027 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: 20110127 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101027 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: 20110228 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: 20101027 Ref country code: SI 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: 20101027 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: 20101027 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: 20110227 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE 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: 20101027 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: 20110128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110207 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: 20101027 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: 20101027 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20101027 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: 20101027 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: 20101027 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: 20101027 |
|
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: 20110728 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602005024423 Country of ref document: DE Effective date: 20110728 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20110831 |
|
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: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110831 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110831 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20120430 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20101027 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20101027 |
|
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 Effective date: 20101027 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230711 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240627 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240702 Year of fee payment: 20 |