CA2117513C - Flame retardant, light stable composition - Google Patents
Flame retardant, light stable compositionInfo
- Publication number
- CA2117513C CA2117513C CA002117513A CA2117513A CA2117513C CA 2117513 C CA2117513 C CA 2117513C CA 002117513 A CA002117513 A CA 002117513A CA 2117513 A CA2117513 A CA 2117513A CA 2117513 C CA2117513 C CA 2117513C
- Authority
- CA
- Canada
- Prior art keywords
- phosphate
- composition
- fiber
- hindered amine
- textile structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 134
- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 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 claims abstract description 44
- 239000000835 fiber Substances 0.000 claims abstract description 119
- 150000001412 amines Chemical class 0.000 claims abstract description 83
- -1 halogenated hydrocarbyl phosphate Chemical compound 0.000 claims abstract description 67
- 239000004611 light stabiliser Substances 0.000 claims abstract description 67
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 49
- 239000010452 phosphate Substances 0.000 claims abstract description 44
- 229920000098 polyolefin Polymers 0.000 claims abstract description 42
- 239000004753 textile Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000006096 absorbing agent Substances 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- 239000004743 Polypropylene Substances 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 230000014759 maintenance of location Effects 0.000 claims description 17
- 238000010998 test method Methods 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 10
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003386 piperidinyl group Chemical group 0.000 claims description 3
- RMXMITCPGRBNAS-UHFFFAOYSA-N tris(2,4,6-tribromophenyl) phosphate Chemical compound BrC1=CC(Br)=CC(Br)=C1OP(=O)(OC=1C(=CC(Br)=CC=1Br)Br)OC1=C(Br)C=C(Br)C=C1Br RMXMITCPGRBNAS-UHFFFAOYSA-N 0.000 claims description 3
- OZEDYCTUPMFWEP-UHFFFAOYSA-N tris(2,4-dibromophenyl) phosphate Chemical compound BrC1=CC(Br)=CC=C1OP(=O)(OC=1C(=CC(Br)=CC=1)Br)OC1=CC=C(Br)C=C1Br OZEDYCTUPMFWEP-UHFFFAOYSA-N 0.000 claims description 3
- FSDYDBAXNANUQE-UHFFFAOYSA-N tris(2,4-dichlorophenyl) phosphate Chemical compound ClC1=CC(Cl)=CC=C1OP(=O)(OC=1C(=CC(Cl)=CC=1)Cl)OC1=CC=C(Cl)C=C1Cl FSDYDBAXNANUQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 abstract description 36
- 150000002148 esters Chemical class 0.000 abstract description 20
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 4
- 238000009472 formulation Methods 0.000 description 49
- 235000021317 phosphate Nutrition 0.000 description 32
- 238000012360 testing method Methods 0.000 description 28
- 239000003381 stabilizer Substances 0.000 description 26
- 239000002932 luster Substances 0.000 description 25
- 238000006731 degradation reaction Methods 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 description 17
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 description 13
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000008380 degradant Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 238000009960 carding Methods 0.000 description 3
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000001054 red pigment Substances 0.000 description 3
- RBFSNPHHISIOGN-UHFFFAOYSA-N tris(1,1,3-trichloro-2,2-dimethylpropyl) phosphate Chemical compound ClCC(C)(C)C(Cl)(Cl)OP(=O)(OC(Cl)(Cl)C(C)(C)CCl)OC(Cl)(Cl)C(C)(C)CCl RBFSNPHHISIOGN-UHFFFAOYSA-N 0.000 description 3
- LLRGDSPVDXCGIM-UHFFFAOYSA-N tris(1,1-dibromo-3-chloro-2,2-dimethylpropyl) phosphate Chemical compound ClCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CCl)OC(Br)(Br)C(C)(C)CCl LLRGDSPVDXCGIM-UHFFFAOYSA-N 0.000 description 3
- OUWSTQZBWYSZBV-UHFFFAOYSA-N tris(3-bromo-1,1-dichloro-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Cl)(Cl)OP(=O)(OC(Cl)(Cl)C(C)(C)CBr)OC(Cl)(Cl)C(C)(C)CBr OUWSTQZBWYSZBV-UHFFFAOYSA-N 0.000 description 3
- 239000001052 yellow pigment Substances 0.000 description 3
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 206010073306 Exposure to radiation Diseases 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005262 alkoxyamine group Chemical group 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 229940069428 antacid Drugs 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 230000001458 anti-acid effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 229920003247 engineering thermoplastic Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000647 material safety data sheet Toxicity 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 238000009732 tufting Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VPYDVGWWXAYRPP-UHFFFAOYSA-N 1-[2-[[4,6-bis[cyclohexyl-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]amino]-1,3,5-triazin-2-yl]-cyclohexylamino]ethyl]-3,3,5,5-tetramethylpiperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN(C=1N=C(N=C(N=1)N(CCN1C(C(C)(C)NC(C)(C)C1)=O)C1CCCCC1)N(CCN1C(C(C)(C)NC(C)(C)C1)=O)C1CCCCC1)C1CCCCC1 VPYDVGWWXAYRPP-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 description 1
- 229920013665 Ampacet Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- JUGOREOARAHOCO-UHFFFAOYSA-M acetylcholine chloride Chemical compound [Cl-].CC(=O)OCC[N+](C)(C)C JUGOREOARAHOCO-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- VRRIVXLVXXAHJA-UHFFFAOYSA-N tris(2,3,4-tribromophenyl) phosphate Chemical class BrC1=C(Br)C(Br)=CC=C1OP(=O)(OC=1C(=C(Br)C(Br)=CC=1)Br)OC1=CC=C(Br)C(Br)=C1Br VRRIVXLVXXAHJA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Abstract
A flame retardant, light stable composition, prepared from a polyolefin, a halogenated hydrocarbyl phosphate or phosphonate ester flame retardant, and an N-alkoxy hindered amine light stabilizer. Suitable forms, in which the composition may be provided, include fibers, and fabrics prepared from such fibers.
Description
B:\HaleyFa.FRM C~ 21 1 751 3 .
The present invention relates to flame retardant, light stable compositions - particularly fibers and textile structures - and to their preparation.
Flame retardancy has become a major consideration, with respect to materials having industrial, commercial, and household applications. For example, polyolefins, including polyolefin plastics, can be highly flammable; accordingly, for products prepared from these substances - e.g., fibers and fabrics, used in products such as clothing, upholstery, and carpeting - the significance of flame retardancy is especially evident.
one means for imparting flame retardancy to polyolefins is by the incorporation of flame retardant additives; these are generally halogenated. Among the halogenated substances, found to have utility as flame retardants, are halogenated hydrocarbyl phosphate and phosphonate esters.
Such compounds appropriate for this purpose include those disclosed in Japanese Patent Publication No. 48-4374, published February 7, 1973, in U.S. Patent No. 4,714,771, and in Chapter 17, "Brominated Phosphate Ester Flame Retardants for Engineering Thermoplastics", Joseph GREEN, Fire and Polymers - Hazards Identification and Prevention, ACS Symposium Series 425, Gordon R. Nelson, Editor, American ChemiCal Society, Washington, D-C., 1990. Reoflam PB-370 - and Reoflam PB-460, from FMC Corporation, Philadelphia, PA, are commercially available brominated hydrocarbyl phosphate ester flame retardants.
Resistance to degradation by W light, or W light stability, is also a desirable property for polyolefin products - including, as above, those prepared ~rom fibers and fabrics of polyolefins. W light stabilizers are correspondingly likewise incorporated with the polyolefins, to impart this property; suitable such substances include the hindered amine light stabilizers (known in the art as HALS).
To provide the properties of flame retardancy and light stability simultaneously, flame retardants and hindered amine light stabilizers have been employed together in polyolefin compositions. However, the halogenated flame retardants have been found to interfere with the function of hindered amine light stabilizers.
Where this interference occurs, the flame retardant forms acid bodies which react with the amine from the light stabilizer, destroying its ability to stabilize against UV
radiation. Specifically, these acid bodies attack the active sites of the hindered amine, thereby robbing it of its stabilizing function.
Hindered amine light stabilizers which have been found to resist this deleterious interaction are the N-alkoxy hindered amine light stabilizers (also known as "alkoxyamine functional hindered amine light stabilizers"), these being identified as NOR HALS and as alkoxy-blocked HALS, in "A
Novel Nonreactive HALS Boosts Polyolefin Stability", Robert I~A~l 175~13 GRAY, Plastics En~ineerin~, June, 1991, and "UV
_ StabiliZation of Polypropylene Fiber", Robert GRAY, ~ Proceedinqs of Poly~ropylene TechnologY Conference, Clemson University, September 4-5, 1991. These publications disclose combinations of halogenated flame retardants and N-alkoxy hindered amine light stabilizers.
However, another disadvantageous phenomenon associated with halogenated flame retardants is their unfavorable effect upon the luster, or shine, of polyolefin products -particularly, fibers and fabrics. Even where halogenatedflame retardants and N-alkoxy hindered amine light stabilizers, used together, are characterized by significant resistance to the degradation by W light, delustering can still occur, because of the action of the flame retardant.
This delustering prevents effective commercial utilization, because of the need to match fiber and fabric appearance, in color aesthetics.
It has been discovered that where the halogenated hydrocarbyl phosphate and phosphonate ester flame retardants are employed, in combination with a light stabilizer component including N-alkoxy hindered amine, not only is the requisite W light stability achieved, but the delustering resulting from use of other flame retardants does not occur;
this desirable combination of properties results, not only where light stabilization is provided by N-alkoxy hindered amine alone, but also where such N-alkoxy hindered amine is employed in conjunction with other hindered amine light stabilizers. This is of particular benefit, for polyolefin products which have flame retardancy, light stabilization, and color requirements.
~ A 2 ~ ~ 7 ~ ~ 3 The invention pertains to a composition comprising a - polyolefin, a halogenated hydrocarbyl phosphate or ~ phosphonate ester flame retardant, and a light stabilizer, comprising an N-alkoxy hindered amine. Preferred polyolefins include polypropylenes, mixtures of polypropylenes and polyethylenes, and ethylene-propylene copolymers.
Preferred flame retardants include halogenated aromatic phosphate or phosphonate esters, and halogenated aliphatic phosphate or phosphonate esters which have no hydrogenated carbon in a position alpha to a halogen bearing carbon.
Particularly preferred such esters are tris(2,4-dibromophenyl) phosphate, tris(2,4-dichlorophenyl) phosphate, tris(2,4,6-tribromophenyl) phosphate, tris (3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneo-pentyl)phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-dichloroneopentyl)phosphate.
The light stabilizer may further comprise a hindered amine with no N-alkoxy group. In such instance, the relative proportions, of the N-alkoxy hindered amine light stabilizer, and the functional hindered amine light stabilizer with no N-alkoxy group, are such that, after exposure to 200 hours of carbon arc radiation, under the conditions set forth in Test Method AATCC 16A-1990 or ASTM
G23-90, the composition has a tenacity retention of at least 50 percent; preferably, the weight ratio, of the N-alkoxy hindered amine to the nonalkoxyamine hindered amine with no N-alkoxy group, is from about 1:5 to about 5:1.
CA2 ~ i 7513 Among the preferred such hindered amine light stabilizers with no N-alkoxy group are polymethyl propyl 3-oxy-[4(2,2,6,6-tetramethyl)piperidinyl] siloxane, fl i~l ~ fl fl ~
- c-(CH2)2-C~ ~ -(CH2)2-oc-~CH2)2-co (CH2)2 N~o _ n having a number average molecular weight (~) of at least about 2500, R ~N~R
N ~N
\~N~
N ~1 R
where R = -NI~ CH3 C4Hg I
~ A ;~ S 1 3 - N --(CH~)6-- N ~ "
N ~N
I
- H H >~ ~n having a number average molecular weight (~) of at least about 2500, and N~
R 1~N R
whe re R - ~N--( CH2) 2~--H
A preferred N-alkoxy hindered amine light stabilizer is that having the formula CA 2 i 1 75 1 3 '_ ~\ 11 1~l ,-- '' H ~ 7 C a 0 N r ~ C -- ( C H 2 ) a -- C O ~ ~ O C 3 H ~ 7 The composition of the invention may further comprise a W light absorber. Suitable W light absorbers include 2-3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
The halogenated hydrocarbyl phosphate or phosphonate ester flame retardant preferably comprises from about 0.5 to about 15 percent by weight of the composition, and the alkoxyamine functional hindered amine light stabilizer preferably comprises from about 0.01 to about 3 percent by weight of the composition. Where the W light absorber is employed, it preferably comprises from about 0.01 to about 3 percent by weight of the composition.
~ A ~ 5 1 3 The invention further pertains to the foregoing _ composition, in the form of fibers and textile structures.
- Preferred textile structures include the woven, nonwoven, tufted, and knitted fabrics.
s The invention yet further pertains to a method of preparing a fiber comprising the foregoing polyolefin, flame retardant, light stabilizer, and, optionally, light absorber; preferably, the indicated amounts of these components are employed. In this method, a mixture of the polyolefin, flame retardant, and light stabilizer (and, optionally, light absorber) is extruded, to obtain a filament; this filament may be textured, or crimped and cut, to provide the fiber.
In the method of preparing the fiber, the components can be dry-mixed, prior to extrusion. Also, the filament obtained by extrusion can be drawn to a fineness of from about 2 to about 25 dpf, texturized in multifilament form to produce a bulked continuous filament (BCF) yarn, or crimped and cut to produce staple fibers.
Still additionally, the invention pertains to methods of preparing a textile structure, comprising a plurality of fibers made from the foregoing components. Such methods include the extrusion, drawing and texturizing of BCF yarns, and the crimping and cutting of staple fibers, as discussed above, to obtain a plurality of the fibers. The fibers are further processed, to form textile structures. For example, the staple fibers can be carded and needled or thermal bonded to obtain a nonwoven felt.
Also, the staple fibers can be carded and spun into yarns, using textile yarn manufacturing processes for short CA2il71~13 (cotton system) and long length (worsted or woolen system) - staple fibers.
~ Textile spun yarns can then be converted to textile structures by processes of weaving, knitting, and/or tufting.
The compositions of the invention comprise at least one polyolefin, at least one flame retardant, and at least one light - particularly, W light - stabilizer. Optionally, at least one W light absorber may also be included, to provide further protection, in addition to that afforded by the light stabilizer, against the polyolefin degradation effected by W light; in this regard, it is noted that the W light absorbers and stabilizers serve the same purpose, but operate by different mechanisms.
Specifically, in acting upon the polyolefin, W light causes degradation by generating free radicals in the polymer chains. The free radicals further attack the chains, breaking them into smaller pieces, and generating additional free radicals, which accelerate this degradation process.
The light stabilizers interfere with this process by reacting with the free radicals produced by the action of the W light on the polymer chains. In this manner, the thusly generated free radicals are prevented from facilitating the degradation process.
In contrast, the W light absorbers absorb the W light and release heat. From such activity, the W light is prevented even from generating the free radicals.
To serve their intended function, W light absorbers must be positioned to interact with the W light - i.e., to interrupt its path - before it can contact, and therefore _g_ act upon, the polyolefin which is to be protected; W
_ absorbers provide no benefit against the activity of - already-generated free radicals. Accordingly, to be effective, W absorbers must be close to the W light receiving surface, of the composition in which they are incorporated - in the case of fibers, and textile structures prepared therefrom, at the fiber surface.
Because of the foregoing, W light absorbers, by themselves, are not completely effective in such fibers and structures, against W light degradation. The reason is that, with the blending of the materials - including polyolefin, and W light absorber - used to make the fiber, and the subsequent extrusion, the W absorber is correspondingly distributed throughout the fiber, with only a statistical portion in the required place, at the fiber surface.
The surface area of the fiber is relatively extensive, in comparison with its entire volume. To provide adequate protection against W light degradation by W light absorber alone, the amount of W light absorber required would be excessive - by reason of its effect upon the fiber.
Regarding the former matter, so much W light absorber would be required, as to prevent the fiber from being extruded. Accordingly, the W light absorbers, though not suitable for use by themselves - for inhibiting W light degradation, in compositions of the invention - can be used in combination with the W light stabilizers, to enhance the stability imparted by these stabilizers, and to reduce the cost of the fiber.
The polyolefins of the invention include those which are suitable for flame retardant, light stable compositions.
~A~ 17Sl~
Among those polyolefins which may be used are homopolymers ~ and copolymers; in this context, the copolymers are - understood as including both those polymers incorporating two different monomeric units, as well as polymers incorporating three or more different monomeric units, e.g., terpolymers, etc.
Among the olefin monomers suitable, for the polyolefins of the invention, are propylene, ethylene, 1-butene, 2-butene, isobutylene, pentene, hexene, heptene, octene, 2-methylpropene-1, 3-methylbutene-1, 4-methylpentene-1, 4-methylhexene-1, 5-methylhexene-1, bicyclo-(2,2,1)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-1,3, 1-methylpentadiene-1, 3,4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene, and methylstyrene. As indicated, the polyolefins of the invention include the homopolymers, and copolymer combinations, of the foregoing olefin monomers, which are appropriate for flame retardant, light stable compositions.
Particular suitable polyolefins are those polypropylenes (PP), including the atactic, syndiotactic, and isotactic polypropylenes, and polyethylenes (PE), including the low density polyethylenes (LDPE), high density polyethylenes (HDPE), and linear low density polyethylenes (LLDPE), which are thusly suitable for such compositions.
Further suitable polyolefins, among the copolymers, are those ethylene-propylene copolymers, including block copolymers of ethylene and propylene, and random copolymers of ethylene and propylene, which are likewise appropriate for flame retardant, light stable compositions.
A single polyolefin, or two or more polyolefins, may be employed, in whatever relative amounts are suitable for obtaining a product characterized by the properties desired ~_ for a particular purpose; one or more other polymers can be - employed, together with the one or more polyolefins. Where multiple polymers, including the indicated one or more polyolefins, are thusly present, any suitable combinations of the polymers, such as multicomponent (e.g., bicomponent) and multticonstituent (e.g., biconstituent) configurations, may be employed. The types and proportions, of the polymers used, can be readily determined by those of ordinary skill in the art, without undue experimentation.
Where a single polyolefin is employed, polypropylenes are preferred homopolymers, and ethylene-propylene copolymers are preferred copolymers. A preferred mixture is that of one or more polypropylenes, and one or more polyethylenes.
Commercially available isotactic polypropylenes which may be used are Himont PH011, P165, and P128, from Himont U.S.A., Wilmington, DE, and Amoco 4 MFR and 9 MFR pellets, from Amoco Chemical Company, Chicago, IL. These polymers have the properties as indicated below.
Polymer Type Densityl Melt2 Melting g/cm3 Flow Point dg/min Range (~C) Himont PH011 PP .905 20 160-165 Himont P165 PP .905 10 160-165 Himont P128 PP .905 13 160-165 Amoco 4 MFR PP .905 4 160-165 Amoco 9 MFR PP .905 9 160-165 2 ASTM 1238.230~C
Suitable flame retardants of the invention include the halogenated phosphate and phosphonate esters - particularly, the halogenated hydrocarbyl phosphate and phosphonate esters; one or more of these flame retardants can be used, 21 ~5 13 alone or in combination. The phosphate esters are ,,_ pre~erred.
Preferably, halogenation is supplied by bromine, chlorine, iodine, or mixtures thereof. Of these, bromine is particularly preferred.
In this context, "hydrocarbyl" includes both "aromatic" and "aliphatic" - particularly, the hydrocarbyl groups are understood as including the alkyl groups and the aryl groups. Further, "hydrocarbyl" is understood as lo including both nonsubstituted hydrocarbyl groups, and substituted hydrocarbyl groups, with the latter referring to the hydrocarbyl portion bearing additional substituents, besides the carbon and hydrogen, and the indicated halogenation.
Halogenated hydrocarbyl phosphate and phosphonate esters having utility as flame retardants, in the compositions of the invention, include those as disclosed in Japanese Patent Publication No. 48-4374, published February 7, 1973, in U.S. Patents Nos. 3,912,792, 3,974,310, 4,710,530, and 4,714,771, and in Chapter 17, "Brominated Phosphate Ester Flame Retardants for Engineering Thermoplastics", Joseph GREEN, Fire and PolYmers - Hazards Identification and Prevention, ACS Symposium Series 425, Gordon R. Nelson, Editor, American Chemical Society, Washington, D.C., 1990.
Among the suitable halogenated aliphatic phosphate esters are the tris(haloneopentyl)phosphates, particularly the tris(trihaloneopentyl)phosphates, including tris(3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneopentyl) phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-dichloroneopentyl)phosphate. Additional appropriate halogenated aliphatic phosphate esters are those of the formulae B
CA~l 1751 3 O = P- (OCH2CHBrCH2Br) 3 O = P- ( OcH2cH2Br ) 3 0 = P-(OCH )3 CH2Br Halogenated aromatic phosphate esters which may be used include the polyhalopolyaryl phosphates, e.g., the tris(halophenyl) phosphates, including those disclosed in U.S. Patent No. 3,912,792, and the polybromotriphenyl phosphates, including those disclosed in U.S. Patent No.
4,710,530. The tris(tribromophenyl) phosphates are suitable; of these, tris(2,4,6-tribromophenyl) phosphate is preferred.
Additional appropriate specific halogenated aromatic phosphate esters are tris(2,4-dibromophenyl) phosphate and ~
tris(2,4-dichlorophenyl) phosphate.
Specific suitable halogenated aliphatic phosphonate esters include those of the formulae CH2Br CH2Br ,CH- ~ - (OCH )2 CH2Br lo CH2Br CH2Cl CR-~ - (OCH ) 2 CH2Br 'O
CH2Br or their variants. In this regard, these phosphonates become partially converted to the phosphite esters, upon standing.
Of the halogenated hydrocarbyl phosphate and phosphonate esters, both the aromatic esters and the aliphatic esters will perform the flame retardant function.
However, there are toxicity problems associated with certain _ forms of the halogenated phosphate and phosphonate aliphatic - esters - particularly, the brominated phosphate and phosphonate esters.
~pecifically, in such aliphatic esters where there is a hydrogen-bearing, or hydrogenated, carbon in the position alpha to - i.e., immediately adjacent to - a halogen bearing carbon, there will occur an elimination, generating a cancer causing agent. Accordingly, for applications where such toxicity is of concern, these aliphatic phosphate and phosphonate esters cannot be used.
Of the specific aliphatic phosphate and phosphonate esters identified above, the compounds characterized by this disadvantageous feature are those of the formulae O = P-(OCH2CHBrCH2Br) 3 O = P- (OCH2CH2Br) 3 CH2Cl O = P-(OCH )3 CH2Br CH2Br CH2Br , CH- P - (OCH )2 CH2Br 1l \
CH2Br CH2Cl CH~ l CH-P - (OCH ) 2 CH2Br 1l \
~ CH2Br Accordingly, these compounds cannot be employed, where considerations of toxicity must be taken into account.
However, aliphatic esters with only nonhydrogenated carbons - i.e., carbons having no hydrogens bonded thereto -3 ~
in positions alpha to halogen bearing carbons are not characteriZed by the indicated carcinogen-producing feature;
accordingly, these compounds are not precluded from applications where such toxicity must be considered. Of the speci~ic aliphatic phosphate and phosphonate esters identified above, tris(3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneopentyl)phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-dichloroneopentyl)phosphate all lack a hydrogenated carbon alpha to a halogen bearing carbon, and so fall within this class.
Commercially available brominated hydrocarbyl phosphate esters which are suitable for the present invention, and which present no toxicity problems, include the earlier lS indicated Reoflam PR-370 and Reoflam PB-460.
Reoflam PB-370, including 3 percent by weight phosphorus and 70 percent by weight bromine, has the chemical composition and properties as set forth in the September, 1989 technical sheet entitled "KRONITEX PB-370 Brominated Phosphate Flame Retardant", and in Material Safety Data Sheet 19186 97 1, "Kronitex(R) PB-370, Brominated Phosphate Ester", Revision 01, Effective Date November 27, 1990, Printing Date December 17, 1990; these are incorporated herein in their entireties, by reference thereto. Reoflam PB-460, a brominated triaryl phosphate ester including 3.9 percent by weight phosphorus and 60 percent by weight aromatic bromine, has the chemical composition and properties as set forth in the September, 1989 technical sheet entitled "KRONITEX PB-460 Brominated Triaryl Phosphate, CAS No. 2788~ 6", and in Material Safety Data Sheet F 16 50 2, "PB 4~0, Brominated Phosphate Flame Retardant", Revision 00, Effective Date October 22, 1992, Printing Date November 23, 1992 2 7 1 7 5 ~ 5 , _ Suitable light stabilizers of the invention include the hindered amine light stabilizers which are N-alkoxy hindered amine light stabilizers - i.e., identified as NOR HALS, including the succinate-based NOR HALS, and as alkoxy-blocked HALS, in the previously indicated publications "A
Novel Nonreactive HALS Boosts Polyolefin Stability", Robert GRAY, Plastics Enqineerinq, June, 1991, and " W
Stabilization of Polypropylene Fiber", Robert GRAY, Proceedin~s o~ PolYProPYlene TechnoloqY Conference, Clemson University, September 4-5, 1991.
One particular suitable such succinate-based stabilizer is that having the formula ~\ 11 1~l /J~
H~ C~ O --~1~ OC-- ~C11 ~ CO ~ -- OC~ H ,~
This stabilizer is commercially available as Tinuvin- 123, from Ciba-Geigy Corporation, Hawthorne, NY.
The N-alkoxy hindered amine light stabilizers preferably have a molecular weight in the range of 200, or about 200, to 5,000, or about 5,000. Both the liquid state and the solid state N-alkoxy hindered amine light stabilizers are suitable for the present invention; those in the solid state are advantageous, in that liquid handling procedures and equipment are not necessary, where these solid state stabilizers are used for preparing the fibers and textile structures of the invention.
One suitable means for employing the liquid state stabilizers, for the present invention, is by initially forminq a concentrate of the stabilizer, with the form of ~n V
- polyolefin used in the composition. This concentrate, which ~ is in the solid state, is what is employed together with the - polyo}efin, flame retardant, and any other components employed.
The indicated Tinuvin 123 stabilizer of the invention is itself in the liquid state. However, it may be provided in the form of a concentrate, in the manner as set forth above.
A single N-alkoxy hindered amine, or two or more N-alkoxy hindered amines in combination, may be employed as the light stabilizer component. Alternatively, one or more N-alkoxy hindered amines may be used, in combination with one or more other hindered amine light stabilizers with no N-alkoxy groups.
Particularly, the light stabilizer component of the invention is that whose inclusion, in the compositions of the invention, provides a degree of resistance to degradation by W light (i.e., a W light stability) such that, after exposure to radiation, according to one of the standards as set forth below, the composition - especially, in the form of fiber, or textile structure - has a tenacity retention of at least 50%, or at least about 50%. More preferably, this tenacity retention is at least 75%, or at least about 75%; most preferably, at least 90%, or at least about 90%.
Regarding the immediately foregoing reference to standards for radiation treatment, one such applicable standard, for the level of exposure, is 200 hours of carbon arc radiation, under the conditions set forth either in AATCC Test Method 16A-l990, or in ASTM G23-90. Of these two test methods, AATCC Test Method 16A-l990 is preferred, although either is suitable, for this purpose; both test methods are incorporated herein in their entireties, by reference thereto.
2 ~ ~ 7 ~ ~ 3 ~
As a more stringent standard, exposure may be to 639 kJ/m2 of W radiation, under the conditions set forth in Test Method SAE J-1885, 1987-08, This more stringent standard is particularly suitable for certain types of the textile structures, e.g., the nonwoven structures, such as the needled felts, especially those with automotive, marine, and related applications.
In any event, combinations of N-alkoxy hindered amine lo and hindered amine with no N-alkoxy groups, as well N-alkoxy hindered amine alone, which - whatever the standard of radiation exposure employed - meet the indicated level of tenacity retention, are within the scope of the invention.
In such instances where more than one hindered amine is employed - whether multiple N-alkoxy hindered amines alone, or one or more N-alkoxy hindered amines in combination with one or more hindered amines with no N-alkoxy groups - the relative proportions of the different compounds to be used, for accomplishing the intended results of the invention, can be readily determined without undue experimentation, by those of ordinary skill in the art.
Particularly where both one or more N-alkoxy hindered amines, and one or more hindered amines with no N-alkoxy groups, are employed, the weight ratio, of N-alkoxy hindered amine to hindered amine with no N-alkoxy group, preferably ranges from 1:5, or about 1:5, to 5:1, or about 5:1; more preferably, this weight ratio is between 1:3, or about 1:3, and 3:1, or about 3:1. As a matter of particular preference, the weight ratio, of N-alkoxy hindered amine to 3~ hindered amine with no N-alkoxy group, is from 1:2, or about 1:2, to 2:1, or about 2:1.
The hindered amine light stabilizers with no N-alkoxy groups which may be used are those which, in conjunction O- -~ ' ~A:Zl 17513 with N-alkoxy hindered amine, will provide the indicated results.
One such hindered amine light stabilizer is that of the formula 1~l 1 1 ~ 1~l 1~l ~
C ( C H 2 ) 2 C ~ ~--( C H 2 ) 2 ~ C ( C H 2 ) 2 C O ( C H 2 ) 2 ~
having a number average molecular weight (~) of at least about 2500. This stabilizer is commercially available as Tinuvin 622, from Ciba-Geigy Corporation.
Another is that of the formula R ~N yR
H
rR ~N ~,N--~N
N ~N
R
h e r e R - -N ~ C H 3 This stabilizer is commercially available as Chimassorb~
119, from Ciba-Geigy Corporation.
Yet another is that of the formula 2 ~ 3 N - (CHz )~-- N
N ~
- H H ~(/ ~ n /\
having a number average molecular weight (~) of at least about 2500. This stabilizer is commercially available as Chimassorb~ 944, from Ciba-Geigy Corporation.
Still another is that of the formula N ~
0~
where R C}N--(CH7) This stabilizer is commercially available as Good-Rite~
3150, from the B.F~ Goodrich Company, Brecksville, OH.
Still another is polymethyl propyl 3-oxy-[4(2,2,6,6-tetramethyl)piperidinyl] siloxane. This stabilizer is commercially available as ~vasil*299-LM, from EniChem Synthesis SpA, Milano, Italy.
* Denotes Trade Mark -21-r~ ..
~, .
(:~2~t ~75~1~
- The suitable W light absorbers include such components ~ which serve the intended purpose of W light absorption, and ~ are compatible with the compositions of the invention, without interfering with their intended properties and functions. The benzotriazole and hydroxybenzoate light absorbers are examples of those which can be employed; among these are 2-3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole, which is commercially available as Tinuvin- 234, from Ciba-Geigy Corporation, and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, which is commercially available as W-CHEK AM-340, from Ferro Corporation, Bedford, OH.
In the compositions of the invention, the polyolefin is preferably present in an amount of at least about 85 or 86 percent by weight of the composition. Generally, the polyolefin comprises about 90 to 95 percent by weight, or more, of the composition.
The halogenated hydrocarbyl phosphate ester flame retardant is preferably present in an amount of between 0.5 percent, or about 0.5 percent, and 15 percent, or about 15 percent, by weight of the composition; more preferably, in an amount of between 0.5 percent, or about 0.5 percent, and 10 percent, or about 10 percent, by weight of the composition. Still more preferably, the halogenated hydrocarbyl phosphate ester is present in an amount of from 1 percent, or about 1 percent, to 5 percent, or about 5 percent, by weight of the composition; a particularly preferred range is between 2 percent, or about 2 percent, and 5 percent, or about 5 percent, by weight of the composition.
The amount of W light stabilizer - whether N-alkoxy hindered amine alone, or in combination with other stabilizer, such as one or more of those discussed above -is preferably from 0.01 percent, or about 0.01 percent, to 3 percent, or about 3 percent, by weight of the composition.
~ A more preferred range is between 0.2 percent, or about 0.2 - percent, and 1 percent, or about 1 percent, by weight of the composltion.
Where W light absorber is employed, the preferred amount is from 0.01 percent, or about 0.01 percent, to 3 percent, or about 3 percent, by weight of the composition.
More preferably, the amount of W light absorber is between 0.3 percent, or about 0.3 percent, and 2 percent, or about 2 percent, by weight of the composition; as a matter of particular preference, the UV light absorber is present in an amount of between 1 percent, or about 1 percent, and 2 percent, or about 2 percent, by weight of the composition.
Conventional additives, in conventional amounts, can also be included, in the compositions - of the invention.
Suitable such additives include coloring agents, such as dyes and pigments. Examples of colorants which may be employed include white (Anatase TiO2) pigment dispersion, commercially available as 41424 PEMB, from AMPACET
Corporation, Tarrytown, NY, yellow pigment dispersion, commercially available as SCC 4200, from Standridge Color Corporation, Social Circle, GA, yellow pigment dispersion, commercially available as Yellow 3172, also commercially available from Standridge Color Corporation, red pigment dispersion, commercially available as Quinacridone Red 267543, from Color Formulators, Inc., Fairfield, NJ, red pigment dispersion, commercially available as Red PP134, from Indol Color Co., Newark, NJ, and black pigment dispersion, commercially available as 3115 Black Fiber PCC, from Southwest Chemical Services Incorporated, Seabrook, TX.
Other appropriate additives are stabilizers - e.g., melt stabilizers - pro-degradants, antistats, and extrusion aids. A pro-degradant which may be employed is dialkyl peroxide, a commercially available example of which is 2 ~ 3 LupersOl*101, from Pennwalt Corporation, Buffalo, NY; a ~ ~ suitable antistat is polyoxyethanol, a commercially available example of which is Dacospin*HS, from Henkel Corporation, Ambler, PA.
A suitable commercially available melt stabilizer is Ul~ranox 626, from GE Specialty Chemicals, Parkersburg, WV.
A suitable extrusion aid is calcium lactate, commercially available is Pationic 1230, from American Ingredients Company, Kansas City, MO.
Appropriate finishes may be employed for coating the fibers of the invention, e.g., during preparation of the fibers. A suitable commercially available finish is Emerlube 7485B, from Henkel Corporation - Emery Group, Cincinnati, OH, this finish being a mixture of an ethoxylated fatty acid ester and amide.
Regarding the flame retardancy of compositions o~ the invention, one suitable test for measuring this property -particularly, with respect to the fibers, and the textile structures prepared therefrom - is test FMVSS 302, Motor Vehicle Interiors, Federal Register, page 70, Vol. 36, No. 5 -Friday, January 8, 1971.
For this FMVSS 302, Motor Vehicle Interiors test, a burn rate of less than or equal to 1.5 inches/minute, or about 1.5 inches/minute, is considered to be acceptable, for the compositions of the invention. However, it is pr~ferable that the compositions of the invention be self-extinguishing, within the meaning of this test.
Another suitable test, for measuring the flame retardancy of the compositions of the invention, is the Vertical Burn Test. This test involves suspending a test specimen over a flame, and measuring the resulting char length, after flame, and drip burn.
* Denotes Trade Mark .
.~ ' ~
C~2~ ~7~1~
Specifically, for the Vertical Burn Test, two 2 3/4 - inch by 10 inch specimens, of the material to be tested, are - cut, with their long dimension in the direction of the warp.
Each of these specimens is subjected to the testing procedure.
In this procedure, the specimen is placed inside a metal frame, covering both sides of the material.
Specifically, the specimen is placed in a metal holder clamping each long edge of the fabric, leaving the ends free, and exposing a strip 2 inches wide, by 10 inches long.
The thusly framed material is placed in a test cabinet.
The holder and specimen are supported in a vertical position -within a shield which is 12 inches wide, 12 inches deep, and 30 inches high, and has a glass observation window -In this position, the lower end of the specimen is suspended 3/4 inch above the top of a Bunsen-type gas burner, used for lighting the specimen. Provision is made for moving the gas burner into position, after the shield is closed.
The burner includes a tube having a 3/8 inch inside diameter, and with the air supply completely shut off, adjusted to give a luminous flame 1 1/2 inches long;
accordingly, when the burner is lighted, the bottom edge of the test specimen hangs 3/4 of an inch into the flame. The 2S burner is supported in a fixed position, with the barrel of the burner at an angle of 25 degrees from the vertical.
The flame is applied vertically, for 12 seconds, near the middle of the width of the lower end of the specimen.
The flame is then withdrawn, and the duration of flaming on the specimen is noted.
As indicated, this test measures the properties of after burn, drip burn, and char length.
After burn is the length of time, in seconds, that the specimen continues to burn, after the burner has been pulled away from the base of the specimen.
C A 2 i 1 7 5 1 3 Drip burn is the length of time, also in seconds, that _ any product continues to burn, once it has dripped from the - specimen, and landed on the floor of the shield.
Char length is the length of material destruction, and is normally measured from the bottom of the sample, to a horizontal line, above which all material is sound and in its original condition - l.e., unaffected by the flame.
Char length is determined immediately, after all flaming and afterglow on the specimen has ceased.
Materials tested under the Vertical Burn Test are graded by "pass/fail" criteria. For fabrics in the following weight categories, results which are at or below the following levels are considered to be passing.
Fabric Weight After Flame Drip Burn Char Lengths founces/sq. yd.) rsec)' (sec)l (inch)2 (inch)' Over 10 2.0 0 3.5 4.5 Over 6 to 10 2.0 0 4.5 5.5 6 and Under 2.0 0 5.5 6.5 I Maximum for an individual specimen 2 Maximum for the average of two specimens Resistance to degradation by W light (i.e., W light stability) may - consistent with the previous discussion herein, concerning the light stabilizers of the invention -be determined by measuring percent tenacity retention, after exposure to 200 hours of carbon arc radiation, under the conditions set forth in AATCC Test Method 16A-1990 or in ASTM G23-90, or exposure to 639 kJ/m2 of W radiation, under the conditions set forth in Test Method SAE J-1885, 1987-08.
For the purposes as set forth herein - also consistent with the indicated previous discussion - a tenacity retention of 50 percent or better is considered to be passing, i.e., acceptable degradation resistance; like the foregoing flame retardancy tests, these test methods are particularly suited for the fibers and textile structures of the invention.
CA~ 7~l~
As to their W light degradation resi~tance, in terms - of the above-indicated test, the compositions of the - invention preferably have a tenacity retention of at least 50 percent, or at least about 50 percent. Their tenacity retention is, more preferably, at least 75 percent, or at least about 75 percent, and, most preferably, at least 90 percent, or at least about so percent.
Another property pertinent to compositions of the invention - yet again, particularly to the fibers and textile structures - is luster. The luster, e.g., of a fiber, is understood as being the shine or glitter in its appearance; in this context, silk is lustrous, and cotton is not.
One means of measuring a fiber's luster is by the difference in the color shade, when the fiber is viewed from angles 90~ apart. What is involved is the mechanism by which the eye perceives color.
Specifically, the eye divides color into three components - red/green, yellow/blue, and light/dark; there are three types of receptors in the back of the eye, one for each of these components. The light/dark component occupies the z axis, in three dimensional space, and is also identified as the lightness, or L value.
In using these factors for measuring luster, fibers are wound on a card - and, accordingly, lined up side by side.
The fibers are viewed in two directions: along their axes (i.e., proc~ing along their length, in the direction from their beginnings to ends); and in the perpendicular direction (i.e., proceeding from side to side, in the direction 90~ to the initially indicated direction of viewing).
Each of these views provides an L value. Luster is the difference in the two L values, or delta L (~L).
In this regard, L, and therefore luster, will be the difference of shade, in the color perceived from these two C14~1 i 7~3 - views. The more distinction there is between the two shades _ -i.e., the lighter one shade is, in comparison to the other - the greater the luster (the higher the ~L value);
conversely, if the shade of color is the same from both views, then the fiber is dull, with no luster (~L = 0).
Consistent with earlier discussion herein on this point, a significant aspect of the property of luster, with respect to the invention, is that - in contrast to prior art compositions, employing other flame retardants - the presence of brominated hydrocarbyl phosphate ester flame retardants does not deluster the compositions of the invention. Specifically, in prior art compositions, the presence of such other flame retardants removes all, or substantially all, of the luster which would otherwise be present, if the flame retardants were not.
However, in the compositions of the invention, inclusion of the halogenated hydrocarbyl flame retardants generally results in minimal surface luster loss - at most, the degree by which luster is decreased is not sufficient to effect the delustering which occurs with other flame retardants, in prior art compositions. The luster maintenance characterizing the compositions of the invention is demonstrated in the Examples which subsequently follow.
The compositions of the invention can be provided in any suitable form, such as fibers, coatings, films, textile structures (i.e., fabrics) and the like, in accordance with their intended function; in this regard, fibers are understood as encompassing both cut and uncut fibers and filaments, including continuous filaments.
Further in this regard, textile structures are understood as encompassing all manner of fabrics, including woven, nonwoven, knitted, and tufted fabrics. As repeatedly noted herein, preferred forms are the fibers and textile structures prepared from the fibers - particularly with respect to the earlier discussed component weight proportion ~21 i7513 - ranges, and values concerning flame retardancy, UV light ~ stability, and luster.
The compositions of the invention - particularly, the fibers, and the textile structures made therefrom - may be prepared by conventional techniques, with the use of conventional equipment. Specifically with respect to the fibers and textile structures, standard means for effecting extrusion, and subsequent processing, may be employed.
As one appropriate method, the polyolefin, halogenated hydrocarbyl phosphate or phosphonate ester flame retardant, and N-alkoxy hindered amine light stabilizer, and any additional components which may be included - e.g., W light absorber, further additives - may be mechanically blended, such as by dry mixing, before being fed to the extruder.
lS Alternatively, they can simply be fed to the extruder, without such prior blending.
In the extruder, the components are subjected to blending, melting, and heating, then extruded therefrom, in the form of filaments. Such extrusion, with the subsequent processing, may be effected by short spin or long spin, as well as using one step or tws step procedures; in this regard, it is understood that the terms "short spin", "long spin", "one step", and "two step" are all used herein, in accordance with their commonly understood meanings in the art, and that, pursuant to such usage, each of the short spin and long spin may be conducted in either one or two steps.
Consistent with the foregoing, where long spin is employed, filaments from the spinnerette of the extruder fall through a comparatively extensive chimney, before being taken up; in this chimney, cooling is effected by passage of air over the filaments. For short spin, there is less distance between spinnerette and takeup, because the means employed for effecting cooling, by passage of air, do not CA21-1 75~ 3 -require as much space, to obtain the desired result, as is ~ necessary for long spin.
-In the two step process, extrusion and the subsequent processing (i.e., drawing, and whatever further optional treatment may be employed, such as crimping, and/or cutting to obtain staple fiber; or texturing to obtain a bulked continuous filament (BCF) fiber) are conducted as separate steps. Specifically, the cooled filaments are wound, on a bobbin, in the undrawn state, and then subjected to the indicated processing.
By contrast, in the one step process, extrusion and processing are effected in a continuous operation. The cooled fibers are collected on a moving cylinder, then immediately subjected to drawing, and subsequently to any of the indicated additional optional treatment.
As previously noted, both long spin and short spin may each be utilized, for either of the one step or two step processes. However, as a matter of preference, for cut staple fiber, long spin is employed in conjunction with the two step process, and short spin, with the one step process.
For continuous filament (CF) or (BCF) fibers, long spin is used in both one step and two step processes.
Filaments and fibers of the invention may be drawn or undrawn, continuous or cut (i.e., staple), texturized or untexturized (e.g., crimped or uncrimped), colored, or uncolored; with reference to terms commonly understood in the art, the continuous filaments may be provided, e.g., in the form of partly oriented yarn (POY), fully oriented yarn (FOY), continuous filament (CF), and bulked continuous filament (BCF), with conventional techniques being suitable for obtaining these forms. Further, filaments and fibers of the invention may be drawn to whatever fineness is appropriate for the intended purpose; preferably, drawing is effected to provide a fiber size in the range of from 2, or 35about 2, to 25, or about 25, denier per filament (dpf).
CA2t 17~1~
- Correspondingly, filaments and fibers of the invention may be combined into bundles having whatever total yarn denier is appropriate for the intended purpose. In a preferred embodiment, they are combined into bundles having a total yarn denier of 50, or about 50, to 30,000, or about 30,000.
Staple fibers of the invention may be used to prepare textile structures, likewise of the invention. In this regard, such fibers can be made into webs, preferably by carding; further, any of the other known commercial processes, including those employing mechanical, electrical, pneumatic, or hydrodynamic means for assembling fibers into a web - e.g., airlaying, carding/hydroentangling, wetlaying, hydroentangling, and spunbonding (i.e., meltspinning of the fibers directly into fibrous webs, by a spunbonding process) -can also be appropriate for this purpose. The thusly carded fiber may appropriately needled, into nonwoven felt fabric.
Staple fibers of the invention may also be carded and spun into yarns, using a cotton, worsted, or woolen system yarn manufacturing process. These spun yarns and the CF and BCF fibers of the invention can be converted to textile structures, likewise of the invention. In this regard, such fibers can be made into fabrics by the commercially known processes of tufting, knitting, and weaving.
Fibers and textile structures of the invention are suitable for a variety of uses - including, but not limited, to upholstery, carpets, window furnishings (e.g., draperies, casings, linings, blinds), wall coverings, panel cloths, automotive, aircraft, and truck interior furnishings (e.g., trim fabrics, upholstery, load floors and carpet), and marine and recreational vehicle fabrics.
The invention is illustrated by the following Examples, which are provided for the purpose of representation, and are not to be construed as limiting the scope of the - inventiOn. Unless stated otherwise, all percentages, parts, - etc. are by weight.
- For each of the formulations in the subsequent Examples 1-5, dry mixing was effected, by tumble mixing blends including the proportions of polypropylene, halogenated hydrocarbyl phosphate ester flame retardant, hindered amine light stabilizer, and (in specified formulations) W light absorber as set forth therein, as well as the following amounts of further components:
Lupersol 101 pro-degradant 0.0040 wt.
Dacospin HS antistat 0.0250 wt. %
41424 white (Anatase Tio2) pigment dispersion 0.10 wt. %
SCC 4200 yellow pigment dispersion 0.15 wt. %
Quinacridone Red 267543 red pigment dispersion 0.11 wt. %
3115 Black Fiber PPC black pigment dispersion 0.16 wt. %
Ultranox- 626 melt stabilizer 0.10 wt. %
Pationic 1230 extrusion aid and antacid 0.10 wt. %
The resulting powder mixture was gravity fed into an extruder. At the feed throat of the extruder, the mixture was blanketed with nitrogen, before entering the extruder;
therein, the mixture was heated to a melt, extruded, and spun into a delta cross section fiber, at a melt temperature of about 240 to 250~C.
In Examples 1-4, the melt was extruded through a standard 40 hole spinnerette, at a rate of 888 meters per minute, to prepare spin yarn of 42 decitex (dtex), 38 denier per filament (dpf). The fiber threadlines in the quench box were exposed to normal ambient air quench (cross blow).
After quenching, the fibers were coated with 1.0 to 2.0 weight percent Emerlube 7485 finish mixture.
The resulting continuous filament yarn was drawn down to 10 dpf, using a mechanical draw ratio of 3.8x.
In Example 5, the melt was extruded through a 700 hole spinnerette, at a rate of 300 meters per minute, to prepare CA~l i1513 - spin yarn of 8.25 decitex (dtex), 7.5 denier per filament ~- ~dpf). The fiber threadlines in the quench box were exposed - to normal ambient air quench (cross blow).
After quenching, the fibers were coated with 1.0 to 2.0 weight percent Emerluube 7485 finish mixture.
The resulting continuous filament yarn was drawn down to 2.5 dpf, using a mechanical draw ratio of 3.0x.
For Examples 1-5, a small portion of the drawn yarn was set aside, for measuring light stability and luster. The remaining yarn was collected in a tow, and crimped at about 20 crimps per inch (79 crimps per 10 cm), using a stufferbox;
the crimped tow was cut into sections 76 mm long, using a metal die and a hydraulic press.
The thusly cut fibers were carded into a web, using commercially available lab-sized e~uipment. This web was further needled into a flat nonwoven felt fabric, in the weight range of 6 to 10 oz./yd.2, using commercially available equipment from Oskar Dilo Maschinenfabrik, Eberbach, Germany.
For the formulations of Example 6, the blends included polypropylene, halogenated hydrocarbyl phosphate ester flame retardant, and hindered amine light stabilizer, but no W
light absorber. The identities and amounts, of the further components, were as follows:
Lupersol 101 pro-degradant 0.2 wt. %
Dacospin HS antistat 0.85 wt. %
41424 white (Anatase TiO2) pigment dispersion 0.8 wt. %
Yellow 3172 30 percent yellow 5687 0.29 wt. %
Red PP 134 50 percent red BRN 0.07 wt. %
3115 Black Fiber PPC black pigment dispersion 0.10 wt. %
Ultranox 626 melt stabilizer 0.2 wt. %
Pationic- 1230 extrusion aid and antacid 0.2 wt. %
C~ 17513 The processing steps previously set forth, for Examples 5, were likewise employed for Example 6, with the following differences.
With respect to the extrusion phase, a melt temperature of 220 to 230~C. was employed. Further, the melt was spun into a round cross section fiber.
The melt was extruded through a standard 110 hole spinnerette, at a rate of 477 meters per minute, to prepare a spin yarn of 22 decitex (20 dpf).
lo As to the Emerlube 7485-coated fibers, these were wound on a package. The continuous filament yarn was drawn to a 6.7 dtex (6 dpf).
The web obtained from carding was multi-layered. The weight range, of the flat felt into which the web was needled, was 10 to 12 oz./yd.2.
For testing flame retardancy, samples were cut from the needled felts. Both test method FMVSS 302, Motor Vehicle Interiors, and the Vertical Burn Test, were employed for the fabrics of Examples 1-5; with the Example 6 materials, only the Vertical Burn Test was used.
As indicated, the drawn continuous filament fiber was used to test light stability and luster. In preparing test samples, this yarn was wound around 63.5 cm x 63.5 cm (2.5 inch x 2.5 inch) cardboard cards.
The samples for testing tenacity retention were exposed to 639 kJ/m2 of W radiation, under the conditions set forth in test method SAE J-1885, 1987-08. The thusly exposed filaments were then cut from the card, and tested for percent tenacity retention.
CA~, 17~13 Luster, measured only in Examples 1-5, was tested with a _ wound card that was not exposed to W radiation.
In each of the following Examples 1-6, the first of the two tables indicates the proportions of polypropylene resin, halogenated phosphate ester flame retardant, hindered amine light stabilizer, and W light absorber included in the formulations, in addition to the previously indicated components. For Examples 1-5, the second table summarizes the results of the flame retardancy, light stability, and luster tests, for the formulations listed in the first table;
as stated above luster is not measured in Example 6.
Particularly as to the Vertical Burn Test, because, as indicated, the fabrics for Examples 1-5 were in the 6 to 10 oz./yd.2 weight range, the pass/fail criteria were as follows:
After Flame - 2 seconds maximum Average Char Length - 4.5 inches maximum Correspondingly, because the Example 6 fabrics had weights of 10 to 12 oz./yd.2, the pass/fail criteria therefor were as follows:
After Flame - 2 seconds maximum Average Char Length - 3.5 inches maximum In this Example, Tinuvin 123, an N-alkoxy hindered amine light stabilizer of the invention, is the sole light stabilizer employed.
~A~ 17513 r~ fWeigh~ Percent ~'~eigh~ Percent Weight Pèrcent Weight Percent Pul~ 1.~ B., ' Phosph-te Hindered Amine Light W Absorbèr Re~in Ester (PB-370) St bilizer HALS Clinuvin 234) (Hitnonl P128) ¢rmuvin 123) A 99.3 0.0 0.0 0.0 B 94.3 5.0 0.0 0.0 C 98.3 0.0 1.0 0.0 D 96.3 0.0 l.0 2.0 E 96.3 0.0 3.0 0 0 F 94.3 0.0 3.0 2.0 G 96.3 2.0 1.0 0.0 H 93.3 5.0 1.0 0.0 1 0 1 91.3 5.0 1.0 2.0 J 91.3 5.0 3.0 0.0 K 89.3 5.0 3.0 2.0 r~ FMVSS 302 VerL;Cal Ten ci~r Retention Luster Burn R te Burn (% of Or;~ L) ~mtmin) A 2.48 Fail <30 (Too wealc to ten) 3.9 BSolf-r ' ~ ' ~ Pau <30 (Too we lc to ten) 3.3 C 1.57 Fail 70 5.2 D 0.87 FaiJ 86 3.9 E 0.78 Fail 89 5.3 F Self-E-' _ '' 8 Fail 97 4.2 2 0 G sclf-r - _ ~ ' ~ _ nu 64 3.8 H Solf-F _ ' _ PuJ 64 4.0 Self-r ' '' P 85 3.4 J Self-E ' _ ''' ~ Pau 50 2.4 K Self-F ' ~ P-u 8~ 3. I
~ 3 6 ~
CA211~13 The foregoing data demonstrate the deficiencies of those ~- fibers and fabrics not of the in-~ention. For those - formulations without the N-alkoxy hindered amine light stabilizer (A, B), the fibers possessed little resistance to W light degradation, as evidenced by the tenacity retention values for these materials.
Regarding the formulations lacking halogenated hydrocarbyl phosphate ester flame retardant (A, C, D, E, F), the fabrics failed the Vertical Burn Test, in each instance.
As to the FMVSS 302 test method, the results were either failing, or only minimally satisfactory, for all save Formulation F (it is not known why the Formulation F fabrics were "self-extinguishing", and this result appears to be an anomaly).
In contrast, for the formulations of the invention -incorporating both the halogenated hydrocarbyl phosphate ester flame retardant and the N-alkoxy hindered amine light stabilizer (G, H, I, J, K) - the fibers and fabrics demonstrated invariably excellent flame retardancy as well as at least acceptable resistance to UV light degradation, without suffering delustering. This last feature - i.e., pertaining to surface luster - is evidenced by a comparison of the ~L values for the fibers of Formulations C-F, on the one hand, and H-K, on the other.
Each of Formulations C-F corresponds to Formulations H-K, respectively, as to the proportion of stabilizer and absorber; however, the former formulations have no flame retardant, while each of the latter comprises 5 percent by weight, of the brominated phosphate ester. Accordingly, Formulations C and H both have 1 percent of the stabilizer and no absorber, but the former has the flame retardant, CA~ ~ 1 751~
- which the latter lacks; this pattern is repeated for ~ Formulations ~-F and I-K, accordingly providing Formulation - pairings of D and I, E and J, and F and K.
For each such pair, the fibers of the formulation including the hydrocarbyl halogenated phosphate ester flame retardant do indeed have a lower ~L value - and therefore, a lesser luster - than the fibers of the formulation without this component. However, the loss is generally minimal, and even where the difference is greatest - i.e., with Formulations E and J - the ~L distinction between 5.2 and 2.4 represents only about a 50 percent loss, and, accordingly, does not rise to the level of delustering, occurring in the prior art.
In this Example also, the only light stabilizer employed is Tinuvin 123, the previously indicated N-alkoxy hindered amine light stabilizer of the invention.
Fo. ' Weight Percent Weigh~ Percent Wcight Perccnt Weight Percent rOI~r~ r~ Phosph~tcHintcred ~minc Lipt UV Ab-orber Resin Ester (PB-3~0) Stabilizer HALS ~rmuvin 234)(Himont P128) ~uulvin 123) A 983 0.0 1 0 00 B 963 00 1.0 20 C 96.3 0.0 3 0 00 D 943 0.0 3.0 20 E 94.3 2.0 10 2.0 F 94 3 2.0 3.0 0.0 2 5 G 92 3 2.0 3.0 2.0 H 933 - 50 1.0 00 913 50 10 - 2.0 J 913 5.0 30 00 K 893 5.0 30 20 ~ 3 8 ~
CA ~ 1 1 75 1 ~
r~ ,FMVSS 302 V~nic~Telucity Retention Luster Burn RJSO Burn(% of OriBinal) (~L) ~ /nun) A 1.42 F~il 81 4.1 B 0.73 Fail 84 3.1 C 1.74 FJ;I 97 4.3 D 2.21 Fail 98 2.8 E Self-F - _ _ P~s~ 94 2.8 F Self-r ' . ' P~ 95 3 7 G Self-F~ ~ ' ~,3 P~u 92 3.3 HS~lf-F - ~, a P~ 69 2.8 I Self-F ~ 77 2.1 J Self-r~ Ps~ 84 3.4 K Self-r ' _ ''' d P~-- 96 2.4 Here also, for the formulations without the flame retardant (A,B,C,D), the fabrics did not pass the Vertical Burn Test, and, as to the FMVSS 302 test method, either failed, or provided only minimally satisfactory results.
However, for the formulations of the invention (E,F,G,H,I,J,K), incorporating both brominated phosphate ester flame retardant and N-alkoxy hindered amine light stabilizer, the fabrics and fibers exhibited excellent flame retardancy, and at least acceptable - and generally good to excellent - resistance to W light degradation; also, as with the Example 1 formulations, besides the fabrics and fibers of the invention being characterized by these advantageous properties, the fibers did not undergo delustering.
Whereas for Example 1, the comparison with regard to luster is made between two groups of formulations, here, three such groups are employed, these being B-D, E-G, and I-K. Consistent with the previous situation, the first, second and third formulations in each group again have the same proportion of stabilizer and absorber, but differ in the ~ A ~
- amount of flame retardant, in that the amount of this latter ~- component progressively increases, from group to group.
- Accordingly, for instance, the three Formulations B, E, and I
of Example 2, while all comprising 1 percent of the stabilizer and 2 percent of the absorber, have none, 2 percent, and 5 percent of the retardant, respectively. This pattern is repeated, with the two groupings corresponding to B, E, and I being C, F, and J as one such grouping, and D, G, and K as the other grouping.
Corresponding to results obtained in Example 1, the ~L
value does decrease, from formulation to formulation within each of the immediately foregoing three groupings, as the amount of flame retardant of the invention increases.
However, again as with Example 1, the loss is generally minimal, and does not rise to the level of the delustering which occurs in the prior art.
CA2, !75~
~ - EXAMPLE 3 _ Fonnul~tion W~ight PercentWcight PercentW~ight Pcrccnt Weight Perccnt P~ .~J'---B.~ ' ' Phosph~tc Hindered Aminc Li~ht W Ab~orber Re~in Ester (PB-370)St~bilizer HALS ~uvin 234) (Himont Pl28) ~Inuvin l23) A 96.3 0.0 I.0 2.0 8 94.3 2.0 I.0 2.0 rvll ' FMVSS 302 Vcrtic-lTcn~cLq Retention Lu~cr (X of Ori~
un) A 0.8S Fail 96 3.1 B Sclf-F ' U P~u lO0 2.8 Consistent with the previous Examples, with Formulation A lacking the halogenated hydrocarbyl phosphate ester flame retardant, the corresponding fabric failed the Vertical Burn Test, and gave only minimally satisfactory results in the FMVSS 302 test method. However, for Formulation B - the corresponding formulation of the invention, incorporating the halogenated hydrocarbyl phosphate ester flame retardant, as well as the N-alkoxy hindered amine light stabilizer - the fabric and fibers exhibited both excellent flame retardancy and excellent resistance to W light degradation, and delustering did not occur.
For this Example, various hindered amine light stabilizers were employed in the different formulations. None of the formulations employing any of Chimassorb 944, Chimassorb 119, or Good-Rite 3150 includes N-alkoxy hindered amine light stabilizer; accordingly, these formulations are 2 5 not provided with light stabilizer of the invention. In Formulation F, which is the sole formulation of the invention in this Example, N-alkoxy hindered amine alone comprises the light stabilizer component.
CA 2 1 1 7~ 1 3 For-~eight ~eightUeight Percent ~eight ~ mu-Percent PercentHindered Amine Light Stabilizer HALS Percent ~a-PolypropyleneBrominated UV
tionResin Phosph~teChimassorb Chimassorb Tinuvin Goodrite Abaorber (Himcnt P128)~pR-~7n~ 119 123 3150(A~-340) A 98.3 0.0 1.0 0.0 0.0 0.0 0.0 8 98.3 0.0 0.0 1.0 0.0 0.0 0.0 C 98.3 0.0 0.0 0.0 1.0 0.0 0.0 D 96.3 Z.0 1.0 0.0 0.0 0.0 0.0 E 96.3 2.0 0.0 1.0 0.0 0.0 0.0 1 0 F 96.3 2.0 0.0 0.0 1.0 0.0 0.0 G 98.3 0.0 0.0 0.0 0.0 0-5 0-5 H 96.3 2.0 0.0 0.0 0.0 0.5 0.5 rv., ' - FMVSS 302 Vc~tic-l Tcn~cit~r Rclention Luder R te Burn(% of Origi~l~
~tnlmin) A2.12 F-il 74 3.3 B2.41 F~il 75 3.4 C2.23 F il 96 3.6 D0.71 F il 41 2.9 Esclf-r - ~ F il 40 2.8 F Self-r ' _ P~ 87 3.1 2 0 G Self F ' e F~il 79 4.7 HSelf-E ~ ~ ' a P~ 47 4.0 For the formulations lacking the halogenated hydrocarbyl flame retardant (A, B, C, and G), the results were consistent with those of the previous Examples - the fabrics failed both 2 5 the Vertical Burn Test and Test Method FMVSS 302 (as occurred in Example 1, here also there is an anomaly, in that Formulation G tested at "self-extinguishing", though lacking the indicated flame retardant - again, the reason for this result is not known). For the formulation of the invention (F), incorporating both halogenated hydrocarbyl phosphate ester flame retardant, and N-alkoxy hindered amine light stabilizer, the fabric and fibers demonstrated excellent CA2i 17513 flame retardancy and resistance to W light degradation, and ~ did not undergo delustering.
EXAMPLE S
All the formulations herein include both the halogenated s hydrocarbyl phosphate ester flame retardant and the N-alkoxy hindered amine light stabilizer, and the products prepared therefrom are fibers and fabrics of the invention. As earlier noted, for this Example, finer fibers - i.e., of 2.5 dpf - were prepared, rather than the 10 dpf fibers of lo Examples 1-4.
FG~ ' 'Weight PercentWeight PercentWei~ht PerccntWeight Percent P~8" ., ~' B.. ' ' Pho-ph-teHindered Amine Li8ht W Ab orber Redn E ter (P~370) St bilizer HALS ~TiAUViD 234) (Himont P128) (I'inuvin 123) A 93.3 5.0 1.0 0.0 B 89.3 5.0 3.0 2.0 C 91.3 5.0 3.0 0.0 D 94.3 2.0 1.0 2.0 E 96.3 2.0 1.0 0.0 F 92.3 2.0 3.0 2.0 G 94.3 2.0 3.0 0.0 r,. FMVSS 302 Vertic-lTcn ciq Retention Lu tet Burn R te Burn (% of Origin~ L) (in/min) 2 0 ASelf-E - ~ ,Pru 55 4.5 BSelf-r~ P~u 89 2.7 C Self-E-- _ ' d Pau 88 3.1 D Self-E - _ ' ~Prre 8S 2.5 E Self-E _ ' _ nu 80 4.3 2 5 F Self-E _ ~ ' ~ 13 Pau 96 2.2 G Self-E _ ' d P~u 72 3.8 Consistent with the fabrics and fibers of the invention in the previous Examples, here also, the fabrics and fibers - are characterized by excellent flame retardancy, at least~ acceptable - and generally excellent - light stability, and lack of delustering.
s This Example includes formulations of the invention wherein the light stabilizer is N-alkoxy hindered amine alone (Formulation B), or in combination with additional hindered amine (Formulations C, D, E, and J).
Formulation Weight PercentWcight Percent Weight Percent Pu~ B.~ ~ 'Hindercd Aminc Light St bilizer HALS
RcainPhosph~te Ester (Himont P128) (P~370) rmuvin ~ ' Tinuvin A 93.3 3.0 1.0 0.0 0.0 B 93.3 3.0 0.0 0.0 1.0 C 93.3 3.0 0.3 0.0 O.
D 93.3 3.0 0.5 0.0 0.5 E 93.3 3.0 0.7 0.0 0.3 F 92.8 3.0 1.0 0.5 0.0 G 93.3 3.0 0.5 0.5 0.0 H 93.1 3.0 0.7 0.5 0.0 92.8 3.0 1.5 0.0 0.0 J 92.8 3.0 1.0 0.0 0.5 Z O K 96.5 0.0 1.0 0.0 0.0 ~ Formulation Vertical Burn Tenacity Retention (% of Original) A Fail 43 B Pass 75 C Pass 82 D Pass 80 E Pass 70 F Fail 67 G Fail 41 H Fail 54 I Fail 48 J Pass 92 K Fail 36 As can be seen for Formulation K, 6.7 dtex (6 dpf) pigmented fibers lacking flame retardant fail the Vertical Burn Test. For finer deniers, such as 6.7 dtex, resistance to fiber degradation and to flame propagation is harder to obtain, because of the increase in the number of fibers per fabric surface area.
However, even where they are provided in such fine denier, the fibers of the invention exhibit good flame retardancy, as well as good resistance to W degradation.
Such favorable results are achieved both where the stabilizer is N-alkoxy amine alone (Formulation B), or in combination with additional hindered amine (Formulations C, D, E, and J).
The foregoing data demonstrate that, just as where the light stabilizer of the invention is N-alkoxy hindered amine alone, the use of other hindered amine light stabilizer, in combination therewith, likewise provides good results in the invention. The data further demonstrate that stabilizer combinations may be varied, to tailor formulations of the I~-A ~ 5 13 - invention according to various factors - e.g., changes in ~ fiber denier (dtex), fabric application requirements, and ~ cost considerations.
Finally, although the invention has been described with s reference to particular means, materials, and embodiments, it should be noted that the invention is not limited to the particulars disclosed, and extends to all equivalents within the scope of the claims.
The present invention relates to flame retardant, light stable compositions - particularly fibers and textile structures - and to their preparation.
Flame retardancy has become a major consideration, with respect to materials having industrial, commercial, and household applications. For example, polyolefins, including polyolefin plastics, can be highly flammable; accordingly, for products prepared from these substances - e.g., fibers and fabrics, used in products such as clothing, upholstery, and carpeting - the significance of flame retardancy is especially evident.
one means for imparting flame retardancy to polyolefins is by the incorporation of flame retardant additives; these are generally halogenated. Among the halogenated substances, found to have utility as flame retardants, are halogenated hydrocarbyl phosphate and phosphonate esters.
Such compounds appropriate for this purpose include those disclosed in Japanese Patent Publication No. 48-4374, published February 7, 1973, in U.S. Patent No. 4,714,771, and in Chapter 17, "Brominated Phosphate Ester Flame Retardants for Engineering Thermoplastics", Joseph GREEN, Fire and Polymers - Hazards Identification and Prevention, ACS Symposium Series 425, Gordon R. Nelson, Editor, American ChemiCal Society, Washington, D-C., 1990. Reoflam PB-370 - and Reoflam PB-460, from FMC Corporation, Philadelphia, PA, are commercially available brominated hydrocarbyl phosphate ester flame retardants.
Resistance to degradation by W light, or W light stability, is also a desirable property for polyolefin products - including, as above, those prepared ~rom fibers and fabrics of polyolefins. W light stabilizers are correspondingly likewise incorporated with the polyolefins, to impart this property; suitable such substances include the hindered amine light stabilizers (known in the art as HALS).
To provide the properties of flame retardancy and light stability simultaneously, flame retardants and hindered amine light stabilizers have been employed together in polyolefin compositions. However, the halogenated flame retardants have been found to interfere with the function of hindered amine light stabilizers.
Where this interference occurs, the flame retardant forms acid bodies which react with the amine from the light stabilizer, destroying its ability to stabilize against UV
radiation. Specifically, these acid bodies attack the active sites of the hindered amine, thereby robbing it of its stabilizing function.
Hindered amine light stabilizers which have been found to resist this deleterious interaction are the N-alkoxy hindered amine light stabilizers (also known as "alkoxyamine functional hindered amine light stabilizers"), these being identified as NOR HALS and as alkoxy-blocked HALS, in "A
Novel Nonreactive HALS Boosts Polyolefin Stability", Robert I~A~l 175~13 GRAY, Plastics En~ineerin~, June, 1991, and "UV
_ StabiliZation of Polypropylene Fiber", Robert GRAY, ~ Proceedinqs of Poly~ropylene TechnologY Conference, Clemson University, September 4-5, 1991. These publications disclose combinations of halogenated flame retardants and N-alkoxy hindered amine light stabilizers.
However, another disadvantageous phenomenon associated with halogenated flame retardants is their unfavorable effect upon the luster, or shine, of polyolefin products -particularly, fibers and fabrics. Even where halogenatedflame retardants and N-alkoxy hindered amine light stabilizers, used together, are characterized by significant resistance to the degradation by W light, delustering can still occur, because of the action of the flame retardant.
This delustering prevents effective commercial utilization, because of the need to match fiber and fabric appearance, in color aesthetics.
It has been discovered that where the halogenated hydrocarbyl phosphate and phosphonate ester flame retardants are employed, in combination with a light stabilizer component including N-alkoxy hindered amine, not only is the requisite W light stability achieved, but the delustering resulting from use of other flame retardants does not occur;
this desirable combination of properties results, not only where light stabilization is provided by N-alkoxy hindered amine alone, but also where such N-alkoxy hindered amine is employed in conjunction with other hindered amine light stabilizers. This is of particular benefit, for polyolefin products which have flame retardancy, light stabilization, and color requirements.
~ A 2 ~ ~ 7 ~ ~ 3 The invention pertains to a composition comprising a - polyolefin, a halogenated hydrocarbyl phosphate or ~ phosphonate ester flame retardant, and a light stabilizer, comprising an N-alkoxy hindered amine. Preferred polyolefins include polypropylenes, mixtures of polypropylenes and polyethylenes, and ethylene-propylene copolymers.
Preferred flame retardants include halogenated aromatic phosphate or phosphonate esters, and halogenated aliphatic phosphate or phosphonate esters which have no hydrogenated carbon in a position alpha to a halogen bearing carbon.
Particularly preferred such esters are tris(2,4-dibromophenyl) phosphate, tris(2,4-dichlorophenyl) phosphate, tris(2,4,6-tribromophenyl) phosphate, tris (3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneo-pentyl)phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-dichloroneopentyl)phosphate.
The light stabilizer may further comprise a hindered amine with no N-alkoxy group. In such instance, the relative proportions, of the N-alkoxy hindered amine light stabilizer, and the functional hindered amine light stabilizer with no N-alkoxy group, are such that, after exposure to 200 hours of carbon arc radiation, under the conditions set forth in Test Method AATCC 16A-1990 or ASTM
G23-90, the composition has a tenacity retention of at least 50 percent; preferably, the weight ratio, of the N-alkoxy hindered amine to the nonalkoxyamine hindered amine with no N-alkoxy group, is from about 1:5 to about 5:1.
CA2 ~ i 7513 Among the preferred such hindered amine light stabilizers with no N-alkoxy group are polymethyl propyl 3-oxy-[4(2,2,6,6-tetramethyl)piperidinyl] siloxane, fl i~l ~ fl fl ~
- c-(CH2)2-C~ ~ -(CH2)2-oc-~CH2)2-co (CH2)2 N~o _ n having a number average molecular weight (~) of at least about 2500, R ~N~R
N ~N
\~N~
N ~1 R
where R = -NI~ CH3 C4Hg I
~ A ;~ S 1 3 - N --(CH~)6-- N ~ "
N ~N
I
- H H >~ ~n having a number average molecular weight (~) of at least about 2500, and N~
R 1~N R
whe re R - ~N--( CH2) 2~--H
A preferred N-alkoxy hindered amine light stabilizer is that having the formula CA 2 i 1 75 1 3 '_ ~\ 11 1~l ,-- '' H ~ 7 C a 0 N r ~ C -- ( C H 2 ) a -- C O ~ ~ O C 3 H ~ 7 The composition of the invention may further comprise a W light absorber. Suitable W light absorbers include 2-3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
The halogenated hydrocarbyl phosphate or phosphonate ester flame retardant preferably comprises from about 0.5 to about 15 percent by weight of the composition, and the alkoxyamine functional hindered amine light stabilizer preferably comprises from about 0.01 to about 3 percent by weight of the composition. Where the W light absorber is employed, it preferably comprises from about 0.01 to about 3 percent by weight of the composition.
~ A ~ 5 1 3 The invention further pertains to the foregoing _ composition, in the form of fibers and textile structures.
- Preferred textile structures include the woven, nonwoven, tufted, and knitted fabrics.
s The invention yet further pertains to a method of preparing a fiber comprising the foregoing polyolefin, flame retardant, light stabilizer, and, optionally, light absorber; preferably, the indicated amounts of these components are employed. In this method, a mixture of the polyolefin, flame retardant, and light stabilizer (and, optionally, light absorber) is extruded, to obtain a filament; this filament may be textured, or crimped and cut, to provide the fiber.
In the method of preparing the fiber, the components can be dry-mixed, prior to extrusion. Also, the filament obtained by extrusion can be drawn to a fineness of from about 2 to about 25 dpf, texturized in multifilament form to produce a bulked continuous filament (BCF) yarn, or crimped and cut to produce staple fibers.
Still additionally, the invention pertains to methods of preparing a textile structure, comprising a plurality of fibers made from the foregoing components. Such methods include the extrusion, drawing and texturizing of BCF yarns, and the crimping and cutting of staple fibers, as discussed above, to obtain a plurality of the fibers. The fibers are further processed, to form textile structures. For example, the staple fibers can be carded and needled or thermal bonded to obtain a nonwoven felt.
Also, the staple fibers can be carded and spun into yarns, using textile yarn manufacturing processes for short CA2il71~13 (cotton system) and long length (worsted or woolen system) - staple fibers.
~ Textile spun yarns can then be converted to textile structures by processes of weaving, knitting, and/or tufting.
The compositions of the invention comprise at least one polyolefin, at least one flame retardant, and at least one light - particularly, W light - stabilizer. Optionally, at least one W light absorber may also be included, to provide further protection, in addition to that afforded by the light stabilizer, against the polyolefin degradation effected by W light; in this regard, it is noted that the W light absorbers and stabilizers serve the same purpose, but operate by different mechanisms.
Specifically, in acting upon the polyolefin, W light causes degradation by generating free radicals in the polymer chains. The free radicals further attack the chains, breaking them into smaller pieces, and generating additional free radicals, which accelerate this degradation process.
The light stabilizers interfere with this process by reacting with the free radicals produced by the action of the W light on the polymer chains. In this manner, the thusly generated free radicals are prevented from facilitating the degradation process.
In contrast, the W light absorbers absorb the W light and release heat. From such activity, the W light is prevented even from generating the free radicals.
To serve their intended function, W light absorbers must be positioned to interact with the W light - i.e., to interrupt its path - before it can contact, and therefore _g_ act upon, the polyolefin which is to be protected; W
_ absorbers provide no benefit against the activity of - already-generated free radicals. Accordingly, to be effective, W absorbers must be close to the W light receiving surface, of the composition in which they are incorporated - in the case of fibers, and textile structures prepared therefrom, at the fiber surface.
Because of the foregoing, W light absorbers, by themselves, are not completely effective in such fibers and structures, against W light degradation. The reason is that, with the blending of the materials - including polyolefin, and W light absorber - used to make the fiber, and the subsequent extrusion, the W absorber is correspondingly distributed throughout the fiber, with only a statistical portion in the required place, at the fiber surface.
The surface area of the fiber is relatively extensive, in comparison with its entire volume. To provide adequate protection against W light degradation by W light absorber alone, the amount of W light absorber required would be excessive - by reason of its effect upon the fiber.
Regarding the former matter, so much W light absorber would be required, as to prevent the fiber from being extruded. Accordingly, the W light absorbers, though not suitable for use by themselves - for inhibiting W light degradation, in compositions of the invention - can be used in combination with the W light stabilizers, to enhance the stability imparted by these stabilizers, and to reduce the cost of the fiber.
The polyolefins of the invention include those which are suitable for flame retardant, light stable compositions.
~A~ 17Sl~
Among those polyolefins which may be used are homopolymers ~ and copolymers; in this context, the copolymers are - understood as including both those polymers incorporating two different monomeric units, as well as polymers incorporating three or more different monomeric units, e.g., terpolymers, etc.
Among the olefin monomers suitable, for the polyolefins of the invention, are propylene, ethylene, 1-butene, 2-butene, isobutylene, pentene, hexene, heptene, octene, 2-methylpropene-1, 3-methylbutene-1, 4-methylpentene-1, 4-methylhexene-1, 5-methylhexene-1, bicyclo-(2,2,1)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-1,3, 1-methylpentadiene-1, 3,4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene, and methylstyrene. As indicated, the polyolefins of the invention include the homopolymers, and copolymer combinations, of the foregoing olefin monomers, which are appropriate for flame retardant, light stable compositions.
Particular suitable polyolefins are those polypropylenes (PP), including the atactic, syndiotactic, and isotactic polypropylenes, and polyethylenes (PE), including the low density polyethylenes (LDPE), high density polyethylenes (HDPE), and linear low density polyethylenes (LLDPE), which are thusly suitable for such compositions.
Further suitable polyolefins, among the copolymers, are those ethylene-propylene copolymers, including block copolymers of ethylene and propylene, and random copolymers of ethylene and propylene, which are likewise appropriate for flame retardant, light stable compositions.
A single polyolefin, or two or more polyolefins, may be employed, in whatever relative amounts are suitable for obtaining a product characterized by the properties desired ~_ for a particular purpose; one or more other polymers can be - employed, together with the one or more polyolefins. Where multiple polymers, including the indicated one or more polyolefins, are thusly present, any suitable combinations of the polymers, such as multicomponent (e.g., bicomponent) and multticonstituent (e.g., biconstituent) configurations, may be employed. The types and proportions, of the polymers used, can be readily determined by those of ordinary skill in the art, without undue experimentation.
Where a single polyolefin is employed, polypropylenes are preferred homopolymers, and ethylene-propylene copolymers are preferred copolymers. A preferred mixture is that of one or more polypropylenes, and one or more polyethylenes.
Commercially available isotactic polypropylenes which may be used are Himont PH011, P165, and P128, from Himont U.S.A., Wilmington, DE, and Amoco 4 MFR and 9 MFR pellets, from Amoco Chemical Company, Chicago, IL. These polymers have the properties as indicated below.
Polymer Type Densityl Melt2 Melting g/cm3 Flow Point dg/min Range (~C) Himont PH011 PP .905 20 160-165 Himont P165 PP .905 10 160-165 Himont P128 PP .905 13 160-165 Amoco 4 MFR PP .905 4 160-165 Amoco 9 MFR PP .905 9 160-165 2 ASTM 1238.230~C
Suitable flame retardants of the invention include the halogenated phosphate and phosphonate esters - particularly, the halogenated hydrocarbyl phosphate and phosphonate esters; one or more of these flame retardants can be used, 21 ~5 13 alone or in combination. The phosphate esters are ,,_ pre~erred.
Preferably, halogenation is supplied by bromine, chlorine, iodine, or mixtures thereof. Of these, bromine is particularly preferred.
In this context, "hydrocarbyl" includes both "aromatic" and "aliphatic" - particularly, the hydrocarbyl groups are understood as including the alkyl groups and the aryl groups. Further, "hydrocarbyl" is understood as lo including both nonsubstituted hydrocarbyl groups, and substituted hydrocarbyl groups, with the latter referring to the hydrocarbyl portion bearing additional substituents, besides the carbon and hydrogen, and the indicated halogenation.
Halogenated hydrocarbyl phosphate and phosphonate esters having utility as flame retardants, in the compositions of the invention, include those as disclosed in Japanese Patent Publication No. 48-4374, published February 7, 1973, in U.S. Patents Nos. 3,912,792, 3,974,310, 4,710,530, and 4,714,771, and in Chapter 17, "Brominated Phosphate Ester Flame Retardants for Engineering Thermoplastics", Joseph GREEN, Fire and PolYmers - Hazards Identification and Prevention, ACS Symposium Series 425, Gordon R. Nelson, Editor, American Chemical Society, Washington, D.C., 1990.
Among the suitable halogenated aliphatic phosphate esters are the tris(haloneopentyl)phosphates, particularly the tris(trihaloneopentyl)phosphates, including tris(3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneopentyl) phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-dichloroneopentyl)phosphate. Additional appropriate halogenated aliphatic phosphate esters are those of the formulae B
CA~l 1751 3 O = P- (OCH2CHBrCH2Br) 3 O = P- ( OcH2cH2Br ) 3 0 = P-(OCH )3 CH2Br Halogenated aromatic phosphate esters which may be used include the polyhalopolyaryl phosphates, e.g., the tris(halophenyl) phosphates, including those disclosed in U.S. Patent No. 3,912,792, and the polybromotriphenyl phosphates, including those disclosed in U.S. Patent No.
4,710,530. The tris(tribromophenyl) phosphates are suitable; of these, tris(2,4,6-tribromophenyl) phosphate is preferred.
Additional appropriate specific halogenated aromatic phosphate esters are tris(2,4-dibromophenyl) phosphate and ~
tris(2,4-dichlorophenyl) phosphate.
Specific suitable halogenated aliphatic phosphonate esters include those of the formulae CH2Br CH2Br ,CH- ~ - (OCH )2 CH2Br lo CH2Br CH2Cl CR-~ - (OCH ) 2 CH2Br 'O
CH2Br or their variants. In this regard, these phosphonates become partially converted to the phosphite esters, upon standing.
Of the halogenated hydrocarbyl phosphate and phosphonate esters, both the aromatic esters and the aliphatic esters will perform the flame retardant function.
However, there are toxicity problems associated with certain _ forms of the halogenated phosphate and phosphonate aliphatic - esters - particularly, the brominated phosphate and phosphonate esters.
~pecifically, in such aliphatic esters where there is a hydrogen-bearing, or hydrogenated, carbon in the position alpha to - i.e., immediately adjacent to - a halogen bearing carbon, there will occur an elimination, generating a cancer causing agent. Accordingly, for applications where such toxicity is of concern, these aliphatic phosphate and phosphonate esters cannot be used.
Of the specific aliphatic phosphate and phosphonate esters identified above, the compounds characterized by this disadvantageous feature are those of the formulae O = P-(OCH2CHBrCH2Br) 3 O = P- (OCH2CH2Br) 3 CH2Cl O = P-(OCH )3 CH2Br CH2Br CH2Br , CH- P - (OCH )2 CH2Br 1l \
CH2Br CH2Cl CH~ l CH-P - (OCH ) 2 CH2Br 1l \
~ CH2Br Accordingly, these compounds cannot be employed, where considerations of toxicity must be taken into account.
However, aliphatic esters with only nonhydrogenated carbons - i.e., carbons having no hydrogens bonded thereto -3 ~
in positions alpha to halogen bearing carbons are not characteriZed by the indicated carcinogen-producing feature;
accordingly, these compounds are not precluded from applications where such toxicity must be considered. Of the speci~ic aliphatic phosphate and phosphonate esters identified above, tris(3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneopentyl)phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-dichloroneopentyl)phosphate all lack a hydrogenated carbon alpha to a halogen bearing carbon, and so fall within this class.
Commercially available brominated hydrocarbyl phosphate esters which are suitable for the present invention, and which present no toxicity problems, include the earlier lS indicated Reoflam PR-370 and Reoflam PB-460.
Reoflam PB-370, including 3 percent by weight phosphorus and 70 percent by weight bromine, has the chemical composition and properties as set forth in the September, 1989 technical sheet entitled "KRONITEX PB-370 Brominated Phosphate Flame Retardant", and in Material Safety Data Sheet 19186 97 1, "Kronitex(R) PB-370, Brominated Phosphate Ester", Revision 01, Effective Date November 27, 1990, Printing Date December 17, 1990; these are incorporated herein in their entireties, by reference thereto. Reoflam PB-460, a brominated triaryl phosphate ester including 3.9 percent by weight phosphorus and 60 percent by weight aromatic bromine, has the chemical composition and properties as set forth in the September, 1989 technical sheet entitled "KRONITEX PB-460 Brominated Triaryl Phosphate, CAS No. 2788~ 6", and in Material Safety Data Sheet F 16 50 2, "PB 4~0, Brominated Phosphate Flame Retardant", Revision 00, Effective Date October 22, 1992, Printing Date November 23, 1992 2 7 1 7 5 ~ 5 , _ Suitable light stabilizers of the invention include the hindered amine light stabilizers which are N-alkoxy hindered amine light stabilizers - i.e., identified as NOR HALS, including the succinate-based NOR HALS, and as alkoxy-blocked HALS, in the previously indicated publications "A
Novel Nonreactive HALS Boosts Polyolefin Stability", Robert GRAY, Plastics Enqineerinq, June, 1991, and " W
Stabilization of Polypropylene Fiber", Robert GRAY, Proceedin~s o~ PolYProPYlene TechnoloqY Conference, Clemson University, September 4-5, 1991.
One particular suitable such succinate-based stabilizer is that having the formula ~\ 11 1~l /J~
H~ C~ O --~1~ OC-- ~C11 ~ CO ~ -- OC~ H ,~
This stabilizer is commercially available as Tinuvin- 123, from Ciba-Geigy Corporation, Hawthorne, NY.
The N-alkoxy hindered amine light stabilizers preferably have a molecular weight in the range of 200, or about 200, to 5,000, or about 5,000. Both the liquid state and the solid state N-alkoxy hindered amine light stabilizers are suitable for the present invention; those in the solid state are advantageous, in that liquid handling procedures and equipment are not necessary, where these solid state stabilizers are used for preparing the fibers and textile structures of the invention.
One suitable means for employing the liquid state stabilizers, for the present invention, is by initially forminq a concentrate of the stabilizer, with the form of ~n V
- polyolefin used in the composition. This concentrate, which ~ is in the solid state, is what is employed together with the - polyo}efin, flame retardant, and any other components employed.
The indicated Tinuvin 123 stabilizer of the invention is itself in the liquid state. However, it may be provided in the form of a concentrate, in the manner as set forth above.
A single N-alkoxy hindered amine, or two or more N-alkoxy hindered amines in combination, may be employed as the light stabilizer component. Alternatively, one or more N-alkoxy hindered amines may be used, in combination with one or more other hindered amine light stabilizers with no N-alkoxy groups.
Particularly, the light stabilizer component of the invention is that whose inclusion, in the compositions of the invention, provides a degree of resistance to degradation by W light (i.e., a W light stability) such that, after exposure to radiation, according to one of the standards as set forth below, the composition - especially, in the form of fiber, or textile structure - has a tenacity retention of at least 50%, or at least about 50%. More preferably, this tenacity retention is at least 75%, or at least about 75%; most preferably, at least 90%, or at least about 90%.
Regarding the immediately foregoing reference to standards for radiation treatment, one such applicable standard, for the level of exposure, is 200 hours of carbon arc radiation, under the conditions set forth either in AATCC Test Method 16A-l990, or in ASTM G23-90. Of these two test methods, AATCC Test Method 16A-l990 is preferred, although either is suitable, for this purpose; both test methods are incorporated herein in their entireties, by reference thereto.
2 ~ ~ 7 ~ ~ 3 ~
As a more stringent standard, exposure may be to 639 kJ/m2 of W radiation, under the conditions set forth in Test Method SAE J-1885, 1987-08, This more stringent standard is particularly suitable for certain types of the textile structures, e.g., the nonwoven structures, such as the needled felts, especially those with automotive, marine, and related applications.
In any event, combinations of N-alkoxy hindered amine lo and hindered amine with no N-alkoxy groups, as well N-alkoxy hindered amine alone, which - whatever the standard of radiation exposure employed - meet the indicated level of tenacity retention, are within the scope of the invention.
In such instances where more than one hindered amine is employed - whether multiple N-alkoxy hindered amines alone, or one or more N-alkoxy hindered amines in combination with one or more hindered amines with no N-alkoxy groups - the relative proportions of the different compounds to be used, for accomplishing the intended results of the invention, can be readily determined without undue experimentation, by those of ordinary skill in the art.
Particularly where both one or more N-alkoxy hindered amines, and one or more hindered amines with no N-alkoxy groups, are employed, the weight ratio, of N-alkoxy hindered amine to hindered amine with no N-alkoxy group, preferably ranges from 1:5, or about 1:5, to 5:1, or about 5:1; more preferably, this weight ratio is between 1:3, or about 1:3, and 3:1, or about 3:1. As a matter of particular preference, the weight ratio, of N-alkoxy hindered amine to 3~ hindered amine with no N-alkoxy group, is from 1:2, or about 1:2, to 2:1, or about 2:1.
The hindered amine light stabilizers with no N-alkoxy groups which may be used are those which, in conjunction O- -~ ' ~A:Zl 17513 with N-alkoxy hindered amine, will provide the indicated results.
One such hindered amine light stabilizer is that of the formula 1~l 1 1 ~ 1~l 1~l ~
C ( C H 2 ) 2 C ~ ~--( C H 2 ) 2 ~ C ( C H 2 ) 2 C O ( C H 2 ) 2 ~
having a number average molecular weight (~) of at least about 2500. This stabilizer is commercially available as Tinuvin 622, from Ciba-Geigy Corporation.
Another is that of the formula R ~N yR
H
rR ~N ~,N--~N
N ~N
R
h e r e R - -N ~ C H 3 This stabilizer is commercially available as Chimassorb~
119, from Ciba-Geigy Corporation.
Yet another is that of the formula 2 ~ 3 N - (CHz )~-- N
N ~
- H H ~(/ ~ n /\
having a number average molecular weight (~) of at least about 2500. This stabilizer is commercially available as Chimassorb~ 944, from Ciba-Geigy Corporation.
Still another is that of the formula N ~
0~
where R C}N--(CH7) This stabilizer is commercially available as Good-Rite~
3150, from the B.F~ Goodrich Company, Brecksville, OH.
Still another is polymethyl propyl 3-oxy-[4(2,2,6,6-tetramethyl)piperidinyl] siloxane. This stabilizer is commercially available as ~vasil*299-LM, from EniChem Synthesis SpA, Milano, Italy.
* Denotes Trade Mark -21-r~ ..
~, .
(:~2~t ~75~1~
- The suitable W light absorbers include such components ~ which serve the intended purpose of W light absorption, and ~ are compatible with the compositions of the invention, without interfering with their intended properties and functions. The benzotriazole and hydroxybenzoate light absorbers are examples of those which can be employed; among these are 2-3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole, which is commercially available as Tinuvin- 234, from Ciba-Geigy Corporation, and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, which is commercially available as W-CHEK AM-340, from Ferro Corporation, Bedford, OH.
In the compositions of the invention, the polyolefin is preferably present in an amount of at least about 85 or 86 percent by weight of the composition. Generally, the polyolefin comprises about 90 to 95 percent by weight, or more, of the composition.
The halogenated hydrocarbyl phosphate ester flame retardant is preferably present in an amount of between 0.5 percent, or about 0.5 percent, and 15 percent, or about 15 percent, by weight of the composition; more preferably, in an amount of between 0.5 percent, or about 0.5 percent, and 10 percent, or about 10 percent, by weight of the composition. Still more preferably, the halogenated hydrocarbyl phosphate ester is present in an amount of from 1 percent, or about 1 percent, to 5 percent, or about 5 percent, by weight of the composition; a particularly preferred range is between 2 percent, or about 2 percent, and 5 percent, or about 5 percent, by weight of the composition.
The amount of W light stabilizer - whether N-alkoxy hindered amine alone, or in combination with other stabilizer, such as one or more of those discussed above -is preferably from 0.01 percent, or about 0.01 percent, to 3 percent, or about 3 percent, by weight of the composition.
~ A more preferred range is between 0.2 percent, or about 0.2 - percent, and 1 percent, or about 1 percent, by weight of the composltion.
Where W light absorber is employed, the preferred amount is from 0.01 percent, or about 0.01 percent, to 3 percent, or about 3 percent, by weight of the composition.
More preferably, the amount of W light absorber is between 0.3 percent, or about 0.3 percent, and 2 percent, or about 2 percent, by weight of the composition; as a matter of particular preference, the UV light absorber is present in an amount of between 1 percent, or about 1 percent, and 2 percent, or about 2 percent, by weight of the composition.
Conventional additives, in conventional amounts, can also be included, in the compositions - of the invention.
Suitable such additives include coloring agents, such as dyes and pigments. Examples of colorants which may be employed include white (Anatase TiO2) pigment dispersion, commercially available as 41424 PEMB, from AMPACET
Corporation, Tarrytown, NY, yellow pigment dispersion, commercially available as SCC 4200, from Standridge Color Corporation, Social Circle, GA, yellow pigment dispersion, commercially available as Yellow 3172, also commercially available from Standridge Color Corporation, red pigment dispersion, commercially available as Quinacridone Red 267543, from Color Formulators, Inc., Fairfield, NJ, red pigment dispersion, commercially available as Red PP134, from Indol Color Co., Newark, NJ, and black pigment dispersion, commercially available as 3115 Black Fiber PCC, from Southwest Chemical Services Incorporated, Seabrook, TX.
Other appropriate additives are stabilizers - e.g., melt stabilizers - pro-degradants, antistats, and extrusion aids. A pro-degradant which may be employed is dialkyl peroxide, a commercially available example of which is 2 ~ 3 LupersOl*101, from Pennwalt Corporation, Buffalo, NY; a ~ ~ suitable antistat is polyoxyethanol, a commercially available example of which is Dacospin*HS, from Henkel Corporation, Ambler, PA.
A suitable commercially available melt stabilizer is Ul~ranox 626, from GE Specialty Chemicals, Parkersburg, WV.
A suitable extrusion aid is calcium lactate, commercially available is Pationic 1230, from American Ingredients Company, Kansas City, MO.
Appropriate finishes may be employed for coating the fibers of the invention, e.g., during preparation of the fibers. A suitable commercially available finish is Emerlube 7485B, from Henkel Corporation - Emery Group, Cincinnati, OH, this finish being a mixture of an ethoxylated fatty acid ester and amide.
Regarding the flame retardancy of compositions o~ the invention, one suitable test for measuring this property -particularly, with respect to the fibers, and the textile structures prepared therefrom - is test FMVSS 302, Motor Vehicle Interiors, Federal Register, page 70, Vol. 36, No. 5 -Friday, January 8, 1971.
For this FMVSS 302, Motor Vehicle Interiors test, a burn rate of less than or equal to 1.5 inches/minute, or about 1.5 inches/minute, is considered to be acceptable, for the compositions of the invention. However, it is pr~ferable that the compositions of the invention be self-extinguishing, within the meaning of this test.
Another suitable test, for measuring the flame retardancy of the compositions of the invention, is the Vertical Burn Test. This test involves suspending a test specimen over a flame, and measuring the resulting char length, after flame, and drip burn.
* Denotes Trade Mark .
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C~2~ ~7~1~
Specifically, for the Vertical Burn Test, two 2 3/4 - inch by 10 inch specimens, of the material to be tested, are - cut, with their long dimension in the direction of the warp.
Each of these specimens is subjected to the testing procedure.
In this procedure, the specimen is placed inside a metal frame, covering both sides of the material.
Specifically, the specimen is placed in a metal holder clamping each long edge of the fabric, leaving the ends free, and exposing a strip 2 inches wide, by 10 inches long.
The thusly framed material is placed in a test cabinet.
The holder and specimen are supported in a vertical position -within a shield which is 12 inches wide, 12 inches deep, and 30 inches high, and has a glass observation window -In this position, the lower end of the specimen is suspended 3/4 inch above the top of a Bunsen-type gas burner, used for lighting the specimen. Provision is made for moving the gas burner into position, after the shield is closed.
The burner includes a tube having a 3/8 inch inside diameter, and with the air supply completely shut off, adjusted to give a luminous flame 1 1/2 inches long;
accordingly, when the burner is lighted, the bottom edge of the test specimen hangs 3/4 of an inch into the flame. The 2S burner is supported in a fixed position, with the barrel of the burner at an angle of 25 degrees from the vertical.
The flame is applied vertically, for 12 seconds, near the middle of the width of the lower end of the specimen.
The flame is then withdrawn, and the duration of flaming on the specimen is noted.
As indicated, this test measures the properties of after burn, drip burn, and char length.
After burn is the length of time, in seconds, that the specimen continues to burn, after the burner has been pulled away from the base of the specimen.
C A 2 i 1 7 5 1 3 Drip burn is the length of time, also in seconds, that _ any product continues to burn, once it has dripped from the - specimen, and landed on the floor of the shield.
Char length is the length of material destruction, and is normally measured from the bottom of the sample, to a horizontal line, above which all material is sound and in its original condition - l.e., unaffected by the flame.
Char length is determined immediately, after all flaming and afterglow on the specimen has ceased.
Materials tested under the Vertical Burn Test are graded by "pass/fail" criteria. For fabrics in the following weight categories, results which are at or below the following levels are considered to be passing.
Fabric Weight After Flame Drip Burn Char Lengths founces/sq. yd.) rsec)' (sec)l (inch)2 (inch)' Over 10 2.0 0 3.5 4.5 Over 6 to 10 2.0 0 4.5 5.5 6 and Under 2.0 0 5.5 6.5 I Maximum for an individual specimen 2 Maximum for the average of two specimens Resistance to degradation by W light (i.e., W light stability) may - consistent with the previous discussion herein, concerning the light stabilizers of the invention -be determined by measuring percent tenacity retention, after exposure to 200 hours of carbon arc radiation, under the conditions set forth in AATCC Test Method 16A-1990 or in ASTM G23-90, or exposure to 639 kJ/m2 of W radiation, under the conditions set forth in Test Method SAE J-1885, 1987-08.
For the purposes as set forth herein - also consistent with the indicated previous discussion - a tenacity retention of 50 percent or better is considered to be passing, i.e., acceptable degradation resistance; like the foregoing flame retardancy tests, these test methods are particularly suited for the fibers and textile structures of the invention.
CA~ 7~l~
As to their W light degradation resi~tance, in terms - of the above-indicated test, the compositions of the - invention preferably have a tenacity retention of at least 50 percent, or at least about 50 percent. Their tenacity retention is, more preferably, at least 75 percent, or at least about 75 percent, and, most preferably, at least 90 percent, or at least about so percent.
Another property pertinent to compositions of the invention - yet again, particularly to the fibers and textile structures - is luster. The luster, e.g., of a fiber, is understood as being the shine or glitter in its appearance; in this context, silk is lustrous, and cotton is not.
One means of measuring a fiber's luster is by the difference in the color shade, when the fiber is viewed from angles 90~ apart. What is involved is the mechanism by which the eye perceives color.
Specifically, the eye divides color into three components - red/green, yellow/blue, and light/dark; there are three types of receptors in the back of the eye, one for each of these components. The light/dark component occupies the z axis, in three dimensional space, and is also identified as the lightness, or L value.
In using these factors for measuring luster, fibers are wound on a card - and, accordingly, lined up side by side.
The fibers are viewed in two directions: along their axes (i.e., proc~ing along their length, in the direction from their beginnings to ends); and in the perpendicular direction (i.e., proceeding from side to side, in the direction 90~ to the initially indicated direction of viewing).
Each of these views provides an L value. Luster is the difference in the two L values, or delta L (~L).
In this regard, L, and therefore luster, will be the difference of shade, in the color perceived from these two C14~1 i 7~3 - views. The more distinction there is between the two shades _ -i.e., the lighter one shade is, in comparison to the other - the greater the luster (the higher the ~L value);
conversely, if the shade of color is the same from both views, then the fiber is dull, with no luster (~L = 0).
Consistent with earlier discussion herein on this point, a significant aspect of the property of luster, with respect to the invention, is that - in contrast to prior art compositions, employing other flame retardants - the presence of brominated hydrocarbyl phosphate ester flame retardants does not deluster the compositions of the invention. Specifically, in prior art compositions, the presence of such other flame retardants removes all, or substantially all, of the luster which would otherwise be present, if the flame retardants were not.
However, in the compositions of the invention, inclusion of the halogenated hydrocarbyl flame retardants generally results in minimal surface luster loss - at most, the degree by which luster is decreased is not sufficient to effect the delustering which occurs with other flame retardants, in prior art compositions. The luster maintenance characterizing the compositions of the invention is demonstrated in the Examples which subsequently follow.
The compositions of the invention can be provided in any suitable form, such as fibers, coatings, films, textile structures (i.e., fabrics) and the like, in accordance with their intended function; in this regard, fibers are understood as encompassing both cut and uncut fibers and filaments, including continuous filaments.
Further in this regard, textile structures are understood as encompassing all manner of fabrics, including woven, nonwoven, knitted, and tufted fabrics. As repeatedly noted herein, preferred forms are the fibers and textile structures prepared from the fibers - particularly with respect to the earlier discussed component weight proportion ~21 i7513 - ranges, and values concerning flame retardancy, UV light ~ stability, and luster.
The compositions of the invention - particularly, the fibers, and the textile structures made therefrom - may be prepared by conventional techniques, with the use of conventional equipment. Specifically with respect to the fibers and textile structures, standard means for effecting extrusion, and subsequent processing, may be employed.
As one appropriate method, the polyolefin, halogenated hydrocarbyl phosphate or phosphonate ester flame retardant, and N-alkoxy hindered amine light stabilizer, and any additional components which may be included - e.g., W light absorber, further additives - may be mechanically blended, such as by dry mixing, before being fed to the extruder.
lS Alternatively, they can simply be fed to the extruder, without such prior blending.
In the extruder, the components are subjected to blending, melting, and heating, then extruded therefrom, in the form of filaments. Such extrusion, with the subsequent processing, may be effected by short spin or long spin, as well as using one step or tws step procedures; in this regard, it is understood that the terms "short spin", "long spin", "one step", and "two step" are all used herein, in accordance with their commonly understood meanings in the art, and that, pursuant to such usage, each of the short spin and long spin may be conducted in either one or two steps.
Consistent with the foregoing, where long spin is employed, filaments from the spinnerette of the extruder fall through a comparatively extensive chimney, before being taken up; in this chimney, cooling is effected by passage of air over the filaments. For short spin, there is less distance between spinnerette and takeup, because the means employed for effecting cooling, by passage of air, do not CA21-1 75~ 3 -require as much space, to obtain the desired result, as is ~ necessary for long spin.
-In the two step process, extrusion and the subsequent processing (i.e., drawing, and whatever further optional treatment may be employed, such as crimping, and/or cutting to obtain staple fiber; or texturing to obtain a bulked continuous filament (BCF) fiber) are conducted as separate steps. Specifically, the cooled filaments are wound, on a bobbin, in the undrawn state, and then subjected to the indicated processing.
By contrast, in the one step process, extrusion and processing are effected in a continuous operation. The cooled fibers are collected on a moving cylinder, then immediately subjected to drawing, and subsequently to any of the indicated additional optional treatment.
As previously noted, both long spin and short spin may each be utilized, for either of the one step or two step processes. However, as a matter of preference, for cut staple fiber, long spin is employed in conjunction with the two step process, and short spin, with the one step process.
For continuous filament (CF) or (BCF) fibers, long spin is used in both one step and two step processes.
Filaments and fibers of the invention may be drawn or undrawn, continuous or cut (i.e., staple), texturized or untexturized (e.g., crimped or uncrimped), colored, or uncolored; with reference to terms commonly understood in the art, the continuous filaments may be provided, e.g., in the form of partly oriented yarn (POY), fully oriented yarn (FOY), continuous filament (CF), and bulked continuous filament (BCF), with conventional techniques being suitable for obtaining these forms. Further, filaments and fibers of the invention may be drawn to whatever fineness is appropriate for the intended purpose; preferably, drawing is effected to provide a fiber size in the range of from 2, or 35about 2, to 25, or about 25, denier per filament (dpf).
CA2t 17~1~
- Correspondingly, filaments and fibers of the invention may be combined into bundles having whatever total yarn denier is appropriate for the intended purpose. In a preferred embodiment, they are combined into bundles having a total yarn denier of 50, or about 50, to 30,000, or about 30,000.
Staple fibers of the invention may be used to prepare textile structures, likewise of the invention. In this regard, such fibers can be made into webs, preferably by carding; further, any of the other known commercial processes, including those employing mechanical, electrical, pneumatic, or hydrodynamic means for assembling fibers into a web - e.g., airlaying, carding/hydroentangling, wetlaying, hydroentangling, and spunbonding (i.e., meltspinning of the fibers directly into fibrous webs, by a spunbonding process) -can also be appropriate for this purpose. The thusly carded fiber may appropriately needled, into nonwoven felt fabric.
Staple fibers of the invention may also be carded and spun into yarns, using a cotton, worsted, or woolen system yarn manufacturing process. These spun yarns and the CF and BCF fibers of the invention can be converted to textile structures, likewise of the invention. In this regard, such fibers can be made into fabrics by the commercially known processes of tufting, knitting, and weaving.
Fibers and textile structures of the invention are suitable for a variety of uses - including, but not limited, to upholstery, carpets, window furnishings (e.g., draperies, casings, linings, blinds), wall coverings, panel cloths, automotive, aircraft, and truck interior furnishings (e.g., trim fabrics, upholstery, load floors and carpet), and marine and recreational vehicle fabrics.
The invention is illustrated by the following Examples, which are provided for the purpose of representation, and are not to be construed as limiting the scope of the - inventiOn. Unless stated otherwise, all percentages, parts, - etc. are by weight.
- For each of the formulations in the subsequent Examples 1-5, dry mixing was effected, by tumble mixing blends including the proportions of polypropylene, halogenated hydrocarbyl phosphate ester flame retardant, hindered amine light stabilizer, and (in specified formulations) W light absorber as set forth therein, as well as the following amounts of further components:
Lupersol 101 pro-degradant 0.0040 wt.
Dacospin HS antistat 0.0250 wt. %
41424 white (Anatase Tio2) pigment dispersion 0.10 wt. %
SCC 4200 yellow pigment dispersion 0.15 wt. %
Quinacridone Red 267543 red pigment dispersion 0.11 wt. %
3115 Black Fiber PPC black pigment dispersion 0.16 wt. %
Ultranox- 626 melt stabilizer 0.10 wt. %
Pationic 1230 extrusion aid and antacid 0.10 wt. %
The resulting powder mixture was gravity fed into an extruder. At the feed throat of the extruder, the mixture was blanketed with nitrogen, before entering the extruder;
therein, the mixture was heated to a melt, extruded, and spun into a delta cross section fiber, at a melt temperature of about 240 to 250~C.
In Examples 1-4, the melt was extruded through a standard 40 hole spinnerette, at a rate of 888 meters per minute, to prepare spin yarn of 42 decitex (dtex), 38 denier per filament (dpf). The fiber threadlines in the quench box were exposed to normal ambient air quench (cross blow).
After quenching, the fibers were coated with 1.0 to 2.0 weight percent Emerlube 7485 finish mixture.
The resulting continuous filament yarn was drawn down to 10 dpf, using a mechanical draw ratio of 3.8x.
In Example 5, the melt was extruded through a 700 hole spinnerette, at a rate of 300 meters per minute, to prepare CA~l i1513 - spin yarn of 8.25 decitex (dtex), 7.5 denier per filament ~- ~dpf). The fiber threadlines in the quench box were exposed - to normal ambient air quench (cross blow).
After quenching, the fibers were coated with 1.0 to 2.0 weight percent Emerluube 7485 finish mixture.
The resulting continuous filament yarn was drawn down to 2.5 dpf, using a mechanical draw ratio of 3.0x.
For Examples 1-5, a small portion of the drawn yarn was set aside, for measuring light stability and luster. The remaining yarn was collected in a tow, and crimped at about 20 crimps per inch (79 crimps per 10 cm), using a stufferbox;
the crimped tow was cut into sections 76 mm long, using a metal die and a hydraulic press.
The thusly cut fibers were carded into a web, using commercially available lab-sized e~uipment. This web was further needled into a flat nonwoven felt fabric, in the weight range of 6 to 10 oz./yd.2, using commercially available equipment from Oskar Dilo Maschinenfabrik, Eberbach, Germany.
For the formulations of Example 6, the blends included polypropylene, halogenated hydrocarbyl phosphate ester flame retardant, and hindered amine light stabilizer, but no W
light absorber. The identities and amounts, of the further components, were as follows:
Lupersol 101 pro-degradant 0.2 wt. %
Dacospin HS antistat 0.85 wt. %
41424 white (Anatase TiO2) pigment dispersion 0.8 wt. %
Yellow 3172 30 percent yellow 5687 0.29 wt. %
Red PP 134 50 percent red BRN 0.07 wt. %
3115 Black Fiber PPC black pigment dispersion 0.10 wt. %
Ultranox 626 melt stabilizer 0.2 wt. %
Pationic- 1230 extrusion aid and antacid 0.2 wt. %
C~ 17513 The processing steps previously set forth, for Examples 5, were likewise employed for Example 6, with the following differences.
With respect to the extrusion phase, a melt temperature of 220 to 230~C. was employed. Further, the melt was spun into a round cross section fiber.
The melt was extruded through a standard 110 hole spinnerette, at a rate of 477 meters per minute, to prepare a spin yarn of 22 decitex (20 dpf).
lo As to the Emerlube 7485-coated fibers, these were wound on a package. The continuous filament yarn was drawn to a 6.7 dtex (6 dpf).
The web obtained from carding was multi-layered. The weight range, of the flat felt into which the web was needled, was 10 to 12 oz./yd.2.
For testing flame retardancy, samples were cut from the needled felts. Both test method FMVSS 302, Motor Vehicle Interiors, and the Vertical Burn Test, were employed for the fabrics of Examples 1-5; with the Example 6 materials, only the Vertical Burn Test was used.
As indicated, the drawn continuous filament fiber was used to test light stability and luster. In preparing test samples, this yarn was wound around 63.5 cm x 63.5 cm (2.5 inch x 2.5 inch) cardboard cards.
The samples for testing tenacity retention were exposed to 639 kJ/m2 of W radiation, under the conditions set forth in test method SAE J-1885, 1987-08. The thusly exposed filaments were then cut from the card, and tested for percent tenacity retention.
CA~, 17~13 Luster, measured only in Examples 1-5, was tested with a _ wound card that was not exposed to W radiation.
In each of the following Examples 1-6, the first of the two tables indicates the proportions of polypropylene resin, halogenated phosphate ester flame retardant, hindered amine light stabilizer, and W light absorber included in the formulations, in addition to the previously indicated components. For Examples 1-5, the second table summarizes the results of the flame retardancy, light stability, and luster tests, for the formulations listed in the first table;
as stated above luster is not measured in Example 6.
Particularly as to the Vertical Burn Test, because, as indicated, the fabrics for Examples 1-5 were in the 6 to 10 oz./yd.2 weight range, the pass/fail criteria were as follows:
After Flame - 2 seconds maximum Average Char Length - 4.5 inches maximum Correspondingly, because the Example 6 fabrics had weights of 10 to 12 oz./yd.2, the pass/fail criteria therefor were as follows:
After Flame - 2 seconds maximum Average Char Length - 3.5 inches maximum In this Example, Tinuvin 123, an N-alkoxy hindered amine light stabilizer of the invention, is the sole light stabilizer employed.
~A~ 17513 r~ fWeigh~ Percent ~'~eigh~ Percent Weight Pèrcent Weight Percent Pul~ 1.~ B., ' Phosph-te Hindered Amine Light W Absorbèr Re~in Ester (PB-370) St bilizer HALS Clinuvin 234) (Hitnonl P128) ¢rmuvin 123) A 99.3 0.0 0.0 0.0 B 94.3 5.0 0.0 0.0 C 98.3 0.0 1.0 0.0 D 96.3 0.0 l.0 2.0 E 96.3 0.0 3.0 0 0 F 94.3 0.0 3.0 2.0 G 96.3 2.0 1.0 0.0 H 93.3 5.0 1.0 0.0 1 0 1 91.3 5.0 1.0 2.0 J 91.3 5.0 3.0 0.0 K 89.3 5.0 3.0 2.0 r~ FMVSS 302 VerL;Cal Ten ci~r Retention Luster Burn R te Burn (% of Or;~ L) ~mtmin) A 2.48 Fail <30 (Too wealc to ten) 3.9 BSolf-r ' ~ ' ~ Pau <30 (Too we lc to ten) 3.3 C 1.57 Fail 70 5.2 D 0.87 FaiJ 86 3.9 E 0.78 Fail 89 5.3 F Self-E-' _ '' 8 Fail 97 4.2 2 0 G sclf-r - _ ~ ' ~ _ nu 64 3.8 H Solf-F _ ' _ PuJ 64 4.0 Self-r ' '' P 85 3.4 J Self-E ' _ ''' ~ Pau 50 2.4 K Self-F ' ~ P-u 8~ 3. I
~ 3 6 ~
CA211~13 The foregoing data demonstrate the deficiencies of those ~- fibers and fabrics not of the in-~ention. For those - formulations without the N-alkoxy hindered amine light stabilizer (A, B), the fibers possessed little resistance to W light degradation, as evidenced by the tenacity retention values for these materials.
Regarding the formulations lacking halogenated hydrocarbyl phosphate ester flame retardant (A, C, D, E, F), the fabrics failed the Vertical Burn Test, in each instance.
As to the FMVSS 302 test method, the results were either failing, or only minimally satisfactory, for all save Formulation F (it is not known why the Formulation F fabrics were "self-extinguishing", and this result appears to be an anomaly).
In contrast, for the formulations of the invention -incorporating both the halogenated hydrocarbyl phosphate ester flame retardant and the N-alkoxy hindered amine light stabilizer (G, H, I, J, K) - the fibers and fabrics demonstrated invariably excellent flame retardancy as well as at least acceptable resistance to UV light degradation, without suffering delustering. This last feature - i.e., pertaining to surface luster - is evidenced by a comparison of the ~L values for the fibers of Formulations C-F, on the one hand, and H-K, on the other.
Each of Formulations C-F corresponds to Formulations H-K, respectively, as to the proportion of stabilizer and absorber; however, the former formulations have no flame retardant, while each of the latter comprises 5 percent by weight, of the brominated phosphate ester. Accordingly, Formulations C and H both have 1 percent of the stabilizer and no absorber, but the former has the flame retardant, CA~ ~ 1 751~
- which the latter lacks; this pattern is repeated for ~ Formulations ~-F and I-K, accordingly providing Formulation - pairings of D and I, E and J, and F and K.
For each such pair, the fibers of the formulation including the hydrocarbyl halogenated phosphate ester flame retardant do indeed have a lower ~L value - and therefore, a lesser luster - than the fibers of the formulation without this component. However, the loss is generally minimal, and even where the difference is greatest - i.e., with Formulations E and J - the ~L distinction between 5.2 and 2.4 represents only about a 50 percent loss, and, accordingly, does not rise to the level of delustering, occurring in the prior art.
In this Example also, the only light stabilizer employed is Tinuvin 123, the previously indicated N-alkoxy hindered amine light stabilizer of the invention.
Fo. ' Weight Percent Weigh~ Percent Wcight Perccnt Weight Percent rOI~r~ r~ Phosph~tcHintcred ~minc Lipt UV Ab-orber Resin Ester (PB-3~0) Stabilizer HALS ~rmuvin 234)(Himont P128) ~uulvin 123) A 983 0.0 1 0 00 B 963 00 1.0 20 C 96.3 0.0 3 0 00 D 943 0.0 3.0 20 E 94.3 2.0 10 2.0 F 94 3 2.0 3.0 0.0 2 5 G 92 3 2.0 3.0 2.0 H 933 - 50 1.0 00 913 50 10 - 2.0 J 913 5.0 30 00 K 893 5.0 30 20 ~ 3 8 ~
CA ~ 1 1 75 1 ~
r~ ,FMVSS 302 V~nic~Telucity Retention Luster Burn RJSO Burn(% of OriBinal) (~L) ~ /nun) A 1.42 F~il 81 4.1 B 0.73 Fail 84 3.1 C 1.74 FJ;I 97 4.3 D 2.21 Fail 98 2.8 E Self-F - _ _ P~s~ 94 2.8 F Self-r ' . ' P~ 95 3 7 G Self-F~ ~ ' ~,3 P~u 92 3.3 HS~lf-F - ~, a P~ 69 2.8 I Self-F ~ 77 2.1 J Self-r~ Ps~ 84 3.4 K Self-r ' _ ''' d P~-- 96 2.4 Here also, for the formulations without the flame retardant (A,B,C,D), the fabrics did not pass the Vertical Burn Test, and, as to the FMVSS 302 test method, either failed, or provided only minimally satisfactory results.
However, for the formulations of the invention (E,F,G,H,I,J,K), incorporating both brominated phosphate ester flame retardant and N-alkoxy hindered amine light stabilizer, the fabrics and fibers exhibited excellent flame retardancy, and at least acceptable - and generally good to excellent - resistance to W light degradation; also, as with the Example 1 formulations, besides the fabrics and fibers of the invention being characterized by these advantageous properties, the fibers did not undergo delustering.
Whereas for Example 1, the comparison with regard to luster is made between two groups of formulations, here, three such groups are employed, these being B-D, E-G, and I-K. Consistent with the previous situation, the first, second and third formulations in each group again have the same proportion of stabilizer and absorber, but differ in the ~ A ~
- amount of flame retardant, in that the amount of this latter ~- component progressively increases, from group to group.
- Accordingly, for instance, the three Formulations B, E, and I
of Example 2, while all comprising 1 percent of the stabilizer and 2 percent of the absorber, have none, 2 percent, and 5 percent of the retardant, respectively. This pattern is repeated, with the two groupings corresponding to B, E, and I being C, F, and J as one such grouping, and D, G, and K as the other grouping.
Corresponding to results obtained in Example 1, the ~L
value does decrease, from formulation to formulation within each of the immediately foregoing three groupings, as the amount of flame retardant of the invention increases.
However, again as with Example 1, the loss is generally minimal, and does not rise to the level of the delustering which occurs in the prior art.
CA2, !75~
~ - EXAMPLE 3 _ Fonnul~tion W~ight PercentWcight PercentW~ight Pcrccnt Weight Perccnt P~ .~J'---B.~ ' ' Phosph~tc Hindered Aminc Li~ht W Ab~orber Re~in Ester (PB-370)St~bilizer HALS ~uvin 234) (Himont Pl28) ~Inuvin l23) A 96.3 0.0 I.0 2.0 8 94.3 2.0 I.0 2.0 rvll ' FMVSS 302 Vcrtic-lTcn~cLq Retention Lu~cr (X of Ori~
un) A 0.8S Fail 96 3.1 B Sclf-F ' U P~u lO0 2.8 Consistent with the previous Examples, with Formulation A lacking the halogenated hydrocarbyl phosphate ester flame retardant, the corresponding fabric failed the Vertical Burn Test, and gave only minimally satisfactory results in the FMVSS 302 test method. However, for Formulation B - the corresponding formulation of the invention, incorporating the halogenated hydrocarbyl phosphate ester flame retardant, as well as the N-alkoxy hindered amine light stabilizer - the fabric and fibers exhibited both excellent flame retardancy and excellent resistance to W light degradation, and delustering did not occur.
For this Example, various hindered amine light stabilizers were employed in the different formulations. None of the formulations employing any of Chimassorb 944, Chimassorb 119, or Good-Rite 3150 includes N-alkoxy hindered amine light stabilizer; accordingly, these formulations are 2 5 not provided with light stabilizer of the invention. In Formulation F, which is the sole formulation of the invention in this Example, N-alkoxy hindered amine alone comprises the light stabilizer component.
CA 2 1 1 7~ 1 3 For-~eight ~eightUeight Percent ~eight ~ mu-Percent PercentHindered Amine Light Stabilizer HALS Percent ~a-PolypropyleneBrominated UV
tionResin Phosph~teChimassorb Chimassorb Tinuvin Goodrite Abaorber (Himcnt P128)~pR-~7n~ 119 123 3150(A~-340) A 98.3 0.0 1.0 0.0 0.0 0.0 0.0 8 98.3 0.0 0.0 1.0 0.0 0.0 0.0 C 98.3 0.0 0.0 0.0 1.0 0.0 0.0 D 96.3 Z.0 1.0 0.0 0.0 0.0 0.0 E 96.3 2.0 0.0 1.0 0.0 0.0 0.0 1 0 F 96.3 2.0 0.0 0.0 1.0 0.0 0.0 G 98.3 0.0 0.0 0.0 0.0 0-5 0-5 H 96.3 2.0 0.0 0.0 0.0 0.5 0.5 rv., ' - FMVSS 302 Vc~tic-l Tcn~cit~r Rclention Luder R te Burn(% of Origi~l~
~tnlmin) A2.12 F-il 74 3.3 B2.41 F~il 75 3.4 C2.23 F il 96 3.6 D0.71 F il 41 2.9 Esclf-r - ~ F il 40 2.8 F Self-r ' _ P~ 87 3.1 2 0 G Self F ' e F~il 79 4.7 HSelf-E ~ ~ ' a P~ 47 4.0 For the formulations lacking the halogenated hydrocarbyl flame retardant (A, B, C, and G), the results were consistent with those of the previous Examples - the fabrics failed both 2 5 the Vertical Burn Test and Test Method FMVSS 302 (as occurred in Example 1, here also there is an anomaly, in that Formulation G tested at "self-extinguishing", though lacking the indicated flame retardant - again, the reason for this result is not known). For the formulation of the invention (F), incorporating both halogenated hydrocarbyl phosphate ester flame retardant, and N-alkoxy hindered amine light stabilizer, the fabric and fibers demonstrated excellent CA2i 17513 flame retardancy and resistance to W light degradation, and ~ did not undergo delustering.
EXAMPLE S
All the formulations herein include both the halogenated s hydrocarbyl phosphate ester flame retardant and the N-alkoxy hindered amine light stabilizer, and the products prepared therefrom are fibers and fabrics of the invention. As earlier noted, for this Example, finer fibers - i.e., of 2.5 dpf - were prepared, rather than the 10 dpf fibers of lo Examples 1-4.
FG~ ' 'Weight PercentWeight PercentWei~ht PerccntWeight Percent P~8" ., ~' B.. ' ' Pho-ph-teHindered Amine Li8ht W Ab orber Redn E ter (P~370) St bilizer HALS ~TiAUViD 234) (Himont P128) (I'inuvin 123) A 93.3 5.0 1.0 0.0 B 89.3 5.0 3.0 2.0 C 91.3 5.0 3.0 0.0 D 94.3 2.0 1.0 2.0 E 96.3 2.0 1.0 0.0 F 92.3 2.0 3.0 2.0 G 94.3 2.0 3.0 0.0 r,. FMVSS 302 Vertic-lTcn ciq Retention Lu tet Burn R te Burn (% of Origin~ L) (in/min) 2 0 ASelf-E - ~ ,Pru 55 4.5 BSelf-r~ P~u 89 2.7 C Self-E-- _ ' d Pau 88 3.1 D Self-E - _ ' ~Prre 8S 2.5 E Self-E _ ' _ nu 80 4.3 2 5 F Self-E _ ~ ' ~ 13 Pau 96 2.2 G Self-E _ ' d P~u 72 3.8 Consistent with the fabrics and fibers of the invention in the previous Examples, here also, the fabrics and fibers - are characterized by excellent flame retardancy, at least~ acceptable - and generally excellent - light stability, and lack of delustering.
s This Example includes formulations of the invention wherein the light stabilizer is N-alkoxy hindered amine alone (Formulation B), or in combination with additional hindered amine (Formulations C, D, E, and J).
Formulation Weight PercentWcight Percent Weight Percent Pu~ B.~ ~ 'Hindercd Aminc Light St bilizer HALS
RcainPhosph~te Ester (Himont P128) (P~370) rmuvin ~ ' Tinuvin A 93.3 3.0 1.0 0.0 0.0 B 93.3 3.0 0.0 0.0 1.0 C 93.3 3.0 0.3 0.0 O.
D 93.3 3.0 0.5 0.0 0.5 E 93.3 3.0 0.7 0.0 0.3 F 92.8 3.0 1.0 0.5 0.0 G 93.3 3.0 0.5 0.5 0.0 H 93.1 3.0 0.7 0.5 0.0 92.8 3.0 1.5 0.0 0.0 J 92.8 3.0 1.0 0.0 0.5 Z O K 96.5 0.0 1.0 0.0 0.0 ~ Formulation Vertical Burn Tenacity Retention (% of Original) A Fail 43 B Pass 75 C Pass 82 D Pass 80 E Pass 70 F Fail 67 G Fail 41 H Fail 54 I Fail 48 J Pass 92 K Fail 36 As can be seen for Formulation K, 6.7 dtex (6 dpf) pigmented fibers lacking flame retardant fail the Vertical Burn Test. For finer deniers, such as 6.7 dtex, resistance to fiber degradation and to flame propagation is harder to obtain, because of the increase in the number of fibers per fabric surface area.
However, even where they are provided in such fine denier, the fibers of the invention exhibit good flame retardancy, as well as good resistance to W degradation.
Such favorable results are achieved both where the stabilizer is N-alkoxy amine alone (Formulation B), or in combination with additional hindered amine (Formulations C, D, E, and J).
The foregoing data demonstrate that, just as where the light stabilizer of the invention is N-alkoxy hindered amine alone, the use of other hindered amine light stabilizer, in combination therewith, likewise provides good results in the invention. The data further demonstrate that stabilizer combinations may be varied, to tailor formulations of the I~-A ~ 5 13 - invention according to various factors - e.g., changes in ~ fiber denier (dtex), fabric application requirements, and ~ cost considerations.
Finally, although the invention has been described with s reference to particular means, materials, and embodiments, it should be noted that the invention is not limited to the particulars disclosed, and extends to all equivalents within the scope of the claims.
Claims (20)
1. A composition comprising:
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine.
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine.
2. A fiber comprising:
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine.
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine.
3. A textile structure comprising a plurality of fibers, the fibers comprising:
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine.
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine.
4. A method of preparing a fiber comprising:
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine;
the method comprising an extrusion step, of extruding a mixture of the at least one polyolefin, the at least one flame retardant, and the at least one light stabilizer, to obtain a filament.
(a) at least one polyolefin;
(b) at least one flame retardant, comprising a halogenated hydrocarbyl phosphate or phosphonate ester; and (c) at least one light stabilizer, comprising an N-alkoxy hindered amine;
the method comprising an extrusion step, of extruding a mixture of the at least one polyolefin, the at least one flame retardant, and the at least one light stabilizer, to obtain a filament.
5. The composition, fiber, textile structure or method of any of the preceding claims wherein the halogenated hydrocarbyl phosphate or phosphonate ester comprises a tris(halohydrocarbyl) phosphate or phosphonate ester.
6. The composition, fiber, textile structure or method of any of the preceding claims wherein the at least one polyolefin comprises a polypropylene, a polyethylene, or an ethylene-propylene copolymer.
7. The composition, fiber, textile structure or method of any of the preceding claims wherein the halogenated hydrocarbyl phosphate or phosphonate ester comprises a halogenated aliphatic phosphate or phosphonate ester without a hydrogenated carbon, in a position alpha to a halogen bearing carbon.
8. The composition, fiber, textile structure or method of claim 7, wherein the halogenated aliphatic phosphate or phosphonate ester comprises a member selected from the group consisting of tris(3-bromo-2,2 bis(bromomethyl)propyl) phosphate, tris(trichloroneopentyl)phosphate, tris(chloro-dibromoneopentyl)phosphate, and tris(bromo-chloroneopenty]) phosphate.
9. The composition, fiber, textile structure or method of claims 1-6, wherein the halogenated hydrocarbyl phosphate or phosphonate ester comprises a halogenated aromatic phosphate or phosphonate ester.
10. The composition, fiber, textile structure or method of claim 9, wherein the halogenated aromatic phosphate or phosphonate ester comprises a member selected from the group consisting of tris(2,4-dibromophenyl)phosphate, tris(2,4-dichlorophenyl) phosphate, and tris(2, 4, 6-tribromophenyl) phosphate.
11. The composition, fiber, textile structure or process of any of the preceding claims, wherein the at least one light stabilizer further comprises a hindered amine with no N-alkoxy group, the N-alkoxy hindered amine and the hindered amine with no N-alkoxy group being present in relative proportions such that, after exposure to 200 hours of carbon arc radiation, under the conditions set forth in AATCC Test Method 16A-1990 or in ASTM G23-90, the composition has a tenacity retention of at least 50 percent.
12. The composition, fiber, textile structure or process of claim 11, wherein the weight ratio, of the N-alkoxy hindered amine to the hindered amine with no N-alkoxy group is from about 1:5 to about 5:1.
13. The composition, fiber, textile structure or process of claim 11, wherein the hindered amine with no N-alkoxy group comprises at least one member selected from the group consisting of polymethyl propel 3-oxy-[4(2,2,6,6-tetramethyl) piperidinyl] siloxane, having a number average molecular weight (M n) of at least about 2500, where R = having a number average molecular weight (M n) of at least about 2500, and where R =
14. The composition, fiber, textile structure or process of any of the preceding claims, wherein the halogenated hydrocarbyl phosphate or phosphonate ester comprises from about 0.5 to about 15 percent by weight of the composition.
15. The composition, fiber, textile structure or process of any of the preceding claims, wherein the N-alkoxy hindered amine comprises
16. The composition, fiber, textile structure or process of any of the preceding claims, wherein the at least one light stabilizer comprises from about 0.01 to about 3 percent by weight of the composition.
17. The composition, fiber, textile structure or process of any of the preceding claims, further comprising at least one UV light absorber.
18. The composition, fiber, textile structure or process of claim 17, wherein the at least one UV light absorber comprises a member selected from the group consisting of 2-3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
19. The composition, fiber, textile structure or process of claim 17, wherein the at least one UV light absorber comprises from about 0.01 to about 3 percent by weight of the composition.
20. A fiber is claimed in any of claims 2 and 5-19, which has a fineness of 2 to 25 dpf.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US114,575 | 1993-08-31 | ||
US08/114,575 US5393812A (en) | 1993-08-31 | 1993-08-31 | Flame retardant, light stable composition |
Publications (2)
Publication Number | Publication Date |
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CA2117513A1 CA2117513A1 (en) | 1995-03-01 |
CA2117513C true CA2117513C (en) | 1999-04-13 |
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CA002117513A Expired - Fee Related CA2117513C (en) | 1993-08-31 | 1994-08-16 | Flame retardant, light stable composition |
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US (1) | US5393812A (en) |
CA (1) | CA2117513C (en) |
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US5393812A (en) | 1995-02-28 |
CA2117513A1 (en) | 1995-03-01 |
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