EP0366700B1 - Electrical wire - Google Patents
Electrical wire Download PDFInfo
- Publication number
- EP0366700B1 EP0366700B1 EP88905963A EP88905963A EP0366700B1 EP 0366700 B1 EP0366700 B1 EP 0366700B1 EP 88905963 A EP88905963 A EP 88905963A EP 88905963 A EP88905963 A EP 88905963A EP 0366700 B1 EP0366700 B1 EP 0366700B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wire
- aromatic
- nylon
- units
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- 125000003118 aryl group Chemical group 0.000 claims abstract description 43
- 229920002647 polyamide Polymers 0.000 claims abstract description 26
- 239000004952 Polyamide Substances 0.000 claims abstract description 21
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 229920000728 polyester Polymers 0.000 claims abstract description 17
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 238000010292 electrical insulation Methods 0.000 claims abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 17
- -1 polytetramethylene terephthalate Polymers 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 229920001601 polyetherimide Polymers 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- 239000004677 Nylon Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920000874 polytetramethylene terephthalate Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001174 sulfone group Chemical group 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001230 polyarylate Polymers 0.000 claims description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920001281 polyalkylene Polymers 0.000 claims description 2
- 229920000412 polyarylene Polymers 0.000 claims description 2
- 229920006260 polyaryletherketone Polymers 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 229920000090 poly(aryl ether) Polymers 0.000 claims 2
- 235000011037 adipic acid Nutrition 0.000 claims 1
- 239000001361 adipic acid Substances 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 41
- 238000009413 insulation Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229920001643 poly(ether ketone) Polymers 0.000 description 5
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical class COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical class NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical class FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Chemical group 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- VQMSCGHBKZXMKT-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;oxolane Chemical compound C1CCOC1.O=C1OCCCCOC(=O)C2=CC=C1C=C2 VQMSCGHBKZXMKT-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- DEFCWQPPZCNKIQ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine;benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1.C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 DEFCWQPPZCNKIQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N Cc(cc1)ccc1OC Chemical compound Cc(cc1)ccc1OC CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- NGIIAPPXNSGKFS-UHFFFAOYSA-N Cc(cc1)ccc1Oc(cc1)ccc1Oc1ccc(/C=[O]\C)cc1 Chemical compound Cc(cc1)ccc1Oc(cc1)ccc1Oc1ccc(/C=[O]\C)cc1 NGIIAPPXNSGKFS-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- 241000270722 Crocodylidae Species 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical group CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical group 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LNNWVNGFPYWNQE-GMIGKAJZSA-N desomorphine Chemical compound C1C2=CC=C(O)C3=C2[C@]24CCN(C)[C@H]1[C@@H]2CCC[C@@H]4O3 LNNWVNGFPYWNQE-GMIGKAJZSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001693 poly(ether-ester) Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/427—Polyethers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/305—Polyamides or polyesteramides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2813—Protection against damage caused by electrical, chemical or water tree deterioration
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
Definitions
- This invention relates to electrical wires and especially to wires that employ electrical insulation based on aromatic polymers.
- aromatic polymer insulation have been used for many years in numerous applications.
- wires that employ polyimide wraps or tapes usually bonded with fluoro-polymer adhesive layers have been used extensively as aircraft wire, for both civil and military applications.
- Other examples of aromatic insulation that have been used for equipment wire or "hook-up" wire, air frame wire and in wire harnesses include aromatic polyether ketones, polyether ether ketones, modified polyphenylene oxide, and polyimide amides.
- Highly aromatic polymers have been used successfully in many applications because they have a range of desirable properties especially high strength and toughness, abrasion resistance, temperature resistance, dielectric strength and are often inherently highly flame-retarded.
- insulating material is removed by a vaporization process originated by an electrical discharge without the formation of electrically conductive deposits so that failure of the insulation will not occur until complete puncture of the insulation occurs.
- an electrical wire which comprises an elongate electrical conductor and electrical insulation that comprises:
- the wire according to the invention has the advantage that it can combine the beneficial properties of highly aromatic polymers, e.g. their good electrical breakdown resistance, fire retardancy, temperature stability and mechanical toughness, with good arc-tracking resistance.
- polymers for the inner layer that are relatively inexpensive and light in weight as compared with fluorinated polymers that have been proposed, and which have greater toughness, e.g. greater resistance to cut- through and abrasion together with reduced tendency to wrinkle as compared with polyolefins.
- the polyamide or polyester forming the inner layer has a carbonaceous char residue of not more than 10%, most preferably not more than 5%, especially not more than 2% and most especially substantially zero.
- the char residue of the polymer components in the electrical wire according to the invention can be measured by the method known as thermogravimetric analysis, or TGA, in which a sample of the polymer is heated in nitrogen or other inert atmosphere at a defined rate to a defined temperature and the residual weight, which is composed of char, is recorded.
- the char residue is simply the quantity of this residual char expressed as a percentage of the initial polymer after having taken into account any non polymeric volatile or non-volatile components.
- the char residue values quoted herein are defined as having been measured at 850°C.
- the polymer has a carbon to hydrogen ratio of not more than 1.1, more preferably not more than 1.0, especially not more than 0.75 and most especially not more than 0.65.
- polyester or polyamide it is possible for the polyester or polyamide to include one or more aromatic moieties in addition to its aliphatic moieties, and indeed a number of preferred polymers do so. However the polymer should have sufficient aliphatic nature that the C:H ratio is not too high.
- Preferred polyamides include the nylons, e.g. nylon 46, nylon 6, nylon 7, nylon 66, nylon 610, nylon 611, nylon 612, nylon 11, nylon 12 and nylon 1212 and aliphatic/aromatic polyamides, e.g.
- polyamides based on the condensation of an aromatic dicarboxylic acid and an aliphatic diamene such as polyamides based on the condensation of terephthalic acid with trimethylhexamethylene diamine (preferably containing a mixture of 2,2,4-and 2,4,4-trimethylhexamethylene diamine isomers), polyamides formed from the condensation of one or more bisaminomethylnorbornane isomers with one or more aliphatic, cycloaliphatic or aromatic dicarboxylic acids e.g. terephthalic acid and optionally including one or more amino acid or lactam e.g.
- s-caprolactam comonomers polyamides based on units derived from laurinlactam, isophthalic acid and bis-(4-amino-3-methylcyclohexyl) methane, polyamides based on the condensation of 2,2-bis-(p-aminocyclohexyl) propane with adipic and azeleic acids, and polyamides based on the condensation of trans cyclohexane-1,4-dicarboxylic acid with the trimethylhexamethylene diamine isomers mentioned above.
- polyether-ester amide block copolymers include those based on polyether and polyamide blocks, especially the so called a "polyether-ester amide block copolymers" of repeating unit: wherein A represents a polyamide sequence of average molecular weight in the range of from 300 to 15,000, preferably from 800 to 5000; and B represents a linear or branched polyoxyalkylene sequence of average molecular weight in the range of from 200 to 6000, preferably from 400 to 3000.
- the polyamide sequence is formed from alpha,omega-aminocarboxylic acids, lactams or dia- mine/dicarboxylic acid combinations that include C 4 to C 14 carbon chains
- the polyoxyalkylene sequence is based on ethylene glycol, propylene glycol and/or tetramethylene glycol, and the polyoxyalkylene sequence constitutes from 5 to 85%, especially from 10 to 50% of the total block copolymer by weight.
- the polyesters that are used in the inner layer preferably include those based on a polyalkylene diol, preferably having a least 3 carbon atoms, or cycloaliphatic diol and an aromatic dicarboxylic acid.
- Preferred polyesters include polytetramethylene terephthalate, and cycloaliphatic diol terephthalic acid copolymers e.g. copolymers of terephthalate and isophthalate units with 1,4-cyclohexanedimethyloxy units.
- the polyesters can include polyether esters, for example polyether polyester block copolymers having long chain units of the general formula: and short-chain ester units of the formula
- G is a divalent radical remaining after the removal of terminal hydroxyl groups from a polyalkylene oxide) glycol, preferably a poly (C 2 to C 4 alkylene oxide) having a molecular weight of about 600 to 6000;
- R is a divalent radical remaining after removal of carboxyl groups from at least one dicarboxylic acid having a molecular weight of less than about 300;
- D is a divalent radical remaining after removal of hydroxyl groups from at least one diol having a molecular weight less than 250.
- polyamide or polyester may be blended with one or more other polymers.
- polyamides may be used as blends with the polyesters, polyolefins such as polyethylene, ethylene ethyl acrylate copolymers or styrene/diene block copolymers, and the polyesters may be used as blends with ionomers or the above polymers referred to in connection with polyamides.
- Such polymers include polyketones, polyether ketones, polyether ether ketones, polyether sulphones, polyether ketone/sulphone copolymers, polyether imides and polyphenylene oxides. Blends of different polymers can be used.
- Preferred aromatic polymers are polymers with a melting or softening point of at least 250°C, particularly at least 300°C and which may be crystalline or amorphous. Softening points of amorphous polymers may conveniently be measured by thermomechanical analysis (TMA), in which case the softening point refers to the temperature at which the probe has reached 60% penetration.
- TMA thermomechanical analysis
- the polymers may be wholly aromatic or they may include one or more aliphatic moieties.
- the polymer comprises, and preferably consists essentially of, units of the formula the units being the same or different, wherein Ar represents an unsubstituted or substituted divalent aromatic radical and Q represents -O-, -S-, - S0 2 -, -CO-, -NH-CO- or -COO-, or Ar represents a trivalent radical and Q represents each bond of the Q radical preferably being bonded directly to an aromatic carbon atom.
- One preferred class of polymer comprises the polyphenylene oxides of the repeating unit in which the groups R 1' which may be the same or different, each represents a hydrogen or halogen atom or a hydrocarbon atom having no tertiary alpha carbon atom.
- the aromatic polymer is a crystalline polyarylene ether comprising recurring units of the formula where E is the residue of a dihydric phenol and E' is the residue of an aromatic compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, the E and E' radicals being linked to the -O- radicals through aromatic carbon atoms.
- E is a radical of the formula wherein R 2 is a divalent radical; x is 0 or 1; Y is a radical selected from halogen atoms, alkyl radicals containing 1 to 4 carbon atoms and alkoxy radicals containing 1 to 4 carbon atoms; y is 0, 1, 2, 3 or4; Y' is a radical selected from halogen atoms, alkyl radicals containing 1 to 4 carbon atoms and alkoxy radicals containing 1 to 4 carbon atoms; z is 0, 1, 2, 3 or 4, and E' is a radical of the formula wherein R 3 is a sulphone, carbonyl, vinyl, sulphoxide, azo, saturated fluorocarbon, organic phosphine oxide or ethylidene radical.
- poly-sulphones are those in which y and z are 0, x is 1, R 3 is a sulphone radical and R 2 is a radical of the formula wherein each of R 4 is independently selected from hydrogen atoms; alkyl radicals containing 1 to 4,carbon atoms which may be unsubstituted or substituted by one or more halogen atoms; aryl, alkaryl and aralkyl radicals containing 6 to 10 carbon atoms which may be unsubstituted or substituted by one or more halogen atoms.
- the polymer is a polyether imide or polysulphone imide which comprises recurring units of the formula where Q is -O- or -SO 2 -, Z is a trivalent aromatic radical, R 5 is a divalent aromatic radical and R 6 is a divalent organic radical.
- the aromatic polymer has the general repeat unit:
- polyetherketones that have repeating groups comprising aromatic ether and aromatic ketone groups together with an imide, amide, ester, benzoxazole or benzothiazole group.
- examples of such polymers are those having repeating units of the formula: where R 7 represents an imide, amide or ester group.
- polyarylates that may be used include those that are derived from dihydric phenols and at least one aromatic dicarboxylic acid.
- examples of such polymers include those derived from a dihydric phenol of the general formula in which the groups Y, which may be the same or different, each represent a hydrogen atom, a C 1 to C 4 alkyl group, or a chlorine or bromine atom; b is 0 or an integer from 1 to 4;
- R 8 represents a divalent saturated or unsaturated hydrocarbon group, e.g. an alkylene, alkylidine, cycloalkylene or cycloalkylidine group, an oxygen or sulphur atom or a carbonyl or sulphonyl group; and c is 0 or 1.
- Preferred aromatic polymers consist essentially of repeating units having one of the following formulae wherein each of x, m and n is 0 or 1, with n being 0 when x is 1, p is an integer from 1 to 4, with m being 1 and x being 0 when p is greater than 1, e.g., or or in which units derived wholly from isophthalic acid or terephthalic acid or a mixture of both are present.
- polymers containing aromatic moieties e.g. poly 1,12-dodecamethylene pyromellitimide or 1,13-tri- decamethylene pyromellitimide, as described in U.S. patent No. 3,551,200, may be used.
- Blends of any two or more of the above polymers may be employed as may copolymers based on any two or more of these polymers.
- blends of any of these aromatic polymers with aliphatic polymers e.g. the aliphatic polymers referred to herein may be used.
- aromatic polymers that are used in the wire insulation will have a char residue of at least 30%, some polymers having a char residue of at least 40% and even at least 50%. This does not mean to say that a high char value is desired for its own sake, but simply that good mechanical and physical properties of these aromatic polymers including temperature stability and fire retardancy, are usually associated with high char residues.
- the preferred aromatic polymers will usually have a molar C:H ratio of at least 1.0, preferably at least 1.2, more preferably at least 1.3 and especially at least 1.4.
- the toughest polymers such as the polyaryl ether ketones, which are associated with high char residues, will have C:H ratios greater than 1.5.
- the outer layer will usually consist solely of the aromatic polymer as the polymeric component.
- the wire insulation is substantially free of halogens, since the presence of significant quantities of halogens can cause corrosive and toxic gases to be emitted when the wire is subjected to a fire.
- the wire insulation contains not more than 10% by weight halogens, more preferably not more than 5% by weight halogens and especially substantially no halogens.
- the wire insulation, or at least the inner layer may be cross-linked, for example, by exposure to high energy radiation.
- Radiation cross-linking may be effected by exposure to high energy irradiation such as an electron beam or gamma-rays. Radiation dosages in the range 20 to 800 kGy, preferably 20 to 500 kGy, e.g. 20 to 200 kGy and particularly 40 to 120 kGy are in general appropriate depending on the characteristics of the polymer in question.
- a prorad such as a poly-functional vinyl or allyl compound
- a prorad such as a poly-functional vinyl or allyl compound
- TAIC triallyl isocyanurate
- methylene bis acrylamide, metaphenylene diamine bis maleimide or other crosslinking agents for example as described in U.S. patents Nos. 4,121,001 and 4,176,027, are incorporated into the composition prior to irradiation.
- the insulation may include additional additives, for example reinforcing or non-reinforcing fillers, stabilisers such as ultra-violet stabilisers, antioxidants, acid acceptors and anti-hydrolysis stabilisers, pigments, processing aids such as plasticizers, halogenated or non-halogenated flame retardants e.g. hydrated metal oxides such as alumina trihydrate or magnesium hydroxide, or decabromodiphenyl ether, fungicides and the like.
- stabilisers such as ultra-violet stabilisers, antioxidants, acid acceptors and anti-hydrolysis stabilisers
- pigments processing aids such as plasticizers
- halogenated or non-halogenated flame retardants e.g. hydrated metal oxides such as alumina trihydrate or magnesium hydroxide, or decabromodiphenyl ether, fungicides and the like.
- the wire insulation will consist solely of the polyamide/polyester inner layer and the aromatic outer layer.
- one or more other layers may be present.
- an additional inorganic arc-control layer may be provided directly on the conductor, formed for example by deposition of an inorganic material on the conductor. Such a layer would enable the thickness of the inner insulating layer to be reduced.
- a wet-tracking control layer which will normally have a low carbonaceous char residue e.g.
- the wires and cables according to the invention may be formed by conventional techniques.
- the polymers may be blended with any additional components, in a mixer, pelletised, and then extruded onto a wire conductor.
- the wires may be used individually as equipment or "hook-up" wires, or airframe wires, or in bundles and harnesses, both jacketted and unjacketted, and may be used in multiconductor cables.
- the wires, harnesses or cables may be unscreened or they may be provided with a screen to protect them from electromagnetic interference, as well known in the art.
- flat cables may be formed using the insulation materials according to the invention, either employing flat conductors or round conductors.
- an electrical wire comprises a conductor 11 which may be solid or stranded as shown and is optionally tinned.
- a 100 micrometre thick inner layer 12 (primary insulation) formed from polybutylene terephthalate or a butylene oxide-butylene terephthalate block copolymer is extruded onto the conductors followed by a 100 micrometre thick layer 13 of polyetherketone, polyether ether ketone or a polyaryletherimide.
- layer 12 may be crosslinked by irradiating the wire with high energy electrons to a dose of about 120 kGy.
- This test is designed to simulate what happens when a fault in a wire bundle causes arcing under dry conditions.
- Agraphite rod is used to initiate the arc which causes thermal degradation of the insulation. Continuation of the fault current can only occur through the wire bundle under test due to shorting across adjacent phases through a conductive char, or direct conductor-conductor contact such as might occur if the insulation is totally removed by the duration of the arc.
- FIG. 1 shows the sample set-up.
- a wire bundle 21 is prepared from seven 10cm lengths 22 of 22AWG tinned-copper or nickel-plated copper conductor coated with a layer of the wire insulation under test.
- the bundle 22 is arranged with six wires around one central wire and held together with tie wraps spaced about 5cm apart.
- One of the outer wires is notched circumferentially between the tie wraps to expose 0.5mm bare conductor and one end of each wire is stripped to enable connections to be made via insulating crocodile clips.
- a rod 23 is provided which is made of a spectrographically pure graphite, diameter 4.6mm, with an impurity level not more than 20ppm. It is prepared before each test by sharpening one end using a conventional pencil sharpener of European design to give an angle of 10 degrees off vertical with a tip diameter of 0.4 ⁇ 0.1 mm.
- a 100g weight 24 is clamped onto the top of the rod 23 to maintain contact during the arc initiation and also acts as a device to limit the depth of penetration of the rod by restricting its downward travel.
- the rod passes through a PTFE bush which allows it to slide freely up and down.
- levers enables precise positioning of the rod 23 on the wire bundle 21 which is held securely in place by means of a simple clamp 25 made of an electrically insulating resin and mounted on a block 26 made of the same material.
- the power source can be either:
- the fault current is detected by means of current clamps surrounding the connecting leads and the voltage at failure is measured using a 10:1 voltage probe.
- the transducer signals are fed into a multi-channel digital storage oscilloscope where they can be displayed and manipulated to obtain power curves (voltage x current) and energy (integration of power curve).
- the wire bundle 21 is positioned in the clamp 25 so that the notched wire is uppermost. Adjacent wires of the bundle are connected to different phases of the supply through 7.5A aircraft type circuit breakers, and the central wire is connected directly to neutral. In the case of single phase or d.c. supplies, alternate wires are connected to neutral or the negative terminal, with the remaining wires, including the central wire, connected through circuit breakers to live or the postive terminal.
- the carbon rod is also connected to neutral or the negative terminal and positioned so that the point is in contact with the exposed conductor.
- the gap between the 100g weight and the PTFE bush is adjusted to the diameter of the insulated wire under test using a suitable spacer to limit the penetration of the rod into the sample.
- a voltage probe is connected across the damaged wire and the rod, and current clamps positioned on each of the three phases, or on the wires connected to the live side of the supply.
- a protective screen is placed in front of the test set-up and the power switched on. A material is deemed to pass this test if:
- non-tracking materials will have relatively few spikes in the current trace with a correspondingly low total energy consumed.
- Tracking materials show many spikes usually on all three phases, which are accompanied by violent crepitation and large energy consumption.
- the following wire constructions were prepared by extruding onto 22 AWG nickel plated copper wire unless otherwise stated using a 20mm Baughan extruder. In the cases where a blend has been used, it has been prepared using a Baker Perkins twin-screw extruder, and in all cases the inner layer contained 5% TAIC and was crosslinked by high energy electron irradiation to a dose of 120 kGy. Examples 1 to 5 were tested for dry tracking with a 115 V 50 Hz, single phase power source, and the results are given in Table I. Examples 6 to 12 were tested using 115 V, 400 Hz three phase supply, and the results are given in Table II.
- Polyaryletheretherketone A polymer having the repeat unit of the formula:
- Polyetherimide A polymer having a repeat unit of formula:
- a blend of polytetramethylene terephthalate and a poly(ether-ester) block copolymer comprising approximately 57% by weight polybutylene terephthalate hard blocks and approximately 43% by weight poly(butylene glycol polyether terephthalate) soft blocks in the ratio of 70:30 as the inner insulating layer with 125 ⁇ m of polyaryletheretherketone as the other insulating layer.
- Example 3 As Example 3 with the exception that the inner insulating layer also contains 20% by weight hydrated zinc borate.
- Example 2 100 ⁇ m of the same polyamide as in Example 1 for the inner layer, and 100 ⁇ m of polyaryletheretherketone as the outer layer.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Resistance Heating (AREA)
- Paints Or Removers (AREA)
- Surgical Instruments (AREA)
Abstract
Description
- This invention relates to electrical wires and especially to wires that employ electrical insulation based on aromatic polymers.
- Electrical wire and cable that use aromatic polymer insulation have been used for many years in numerous applications. For example wires that employ polyimide wraps or tapes usually bonded with fluoro-polymer adhesive layers have been used extensively as aircraft wire, for both civil and military applications. Other examples of aromatic insulation that have been used for equipment wire or "hook-up" wire, air frame wire and in wire harnesses include aromatic polyether ketones, polyether ether ketones, modified polyphenylene oxide, and polyimide amides. Highly aromatic polymers have been used successfully in many applications because they have a range of desirable properties especially high strength and toughness, abrasion resistance, temperature resistance, dielectric strength and are often inherently highly flame-retarded.
- The combination of these properties has enabled wire and cable fabricated from these polymers to be used in small lightweight constructions. Such constructions have been used increasingly in both military and civil applications due to the high density and complexity of modern electrical systems.
- However, these highly aromatic polymers suffer from a major problem: they are particularly susceptible to breakdown due to arcing. A potential difference between two conductors, or between a conductor in which the insulation has been mechanically damaged, and ground, can result in the formation of an arc between the conductors or between the conductor and ground. The high temperature of the arc causes the polymer to degrade extremely rapidly and form an electrically conductive carbonaceous deposit which can extend rapidly, and lead to catastrophic failure in which many or all of the wires in a bundle are destroyed. Arcing can occur at very low voltages, for example 24V d.c. or lower, and since, unlike tracking, no electrolyte or moisture is involved, it is a particularly hazardous phenomenon. Arcs may also be struck by drawing apart two conductors between which a current is passing as described for example by J.M. Somerville "The Electric Arc", Methuen 1959.
- Another phenomenon that can be associated with tracking and arcing is erosion. In this case insulating material is removed by a vaporization process originated by an electrical discharge without the formation of electrically conductive deposits so that failure of the insulation will not occur until complete puncture of the insulation occurs.
- According to the present invention there is provided an electrical wire which comprises an elongate electrical conductor and electrical insulation that comprises:
- (a) an inner melt-extruded insulating layer which comprises a polyamide or polyester having aliphatic moieties and having a char residue of not more than 15% by weight; and
- (b) an outer melt-extruded insulating layer which comprises an aromatic polymer.
- The wire according to the invention has the advantage that it can combine the beneficial properties of highly aromatic polymers, e.g. their good electrical breakdown resistance, fire retardancy, temperature stability and mechanical toughness, with good arc-tracking resistance. In addition, it is possible according to the invention to employ polymers for the inner layer that are relatively inexpensive and light in weight as compared with fluorinated polymers that have been proposed, and which have greater toughness, e.g. greater resistance to cut- through and abrasion together with reduced tendency to wrinkle as compared with polyolefins.
- Preferably the polyamide or polyester forming the inner layer has a carbonaceous char residue of not more than 10%, most preferably not more than 5%, especially not more than 2% and most especially substantially zero. The char residue of the polymer components in the electrical wire according to the invention can be measured by the method known as thermogravimetric analysis, or TGA, in which a sample of the polymer is heated in nitrogen or other inert atmosphere at a defined rate to a defined temperature and the residual weight, which is composed of char, is recorded. The char residue is simply the quantity of this residual char expressed as a percentage of the initial polymer after having taken into account any non polymeric volatile or non-volatile components. The char residue values quoted herein are defined as having been measured at 850°C. This will normally be achieved by choosing a polyamide or polyester that has a relatively low molar carbon to hydrogen ratio. Preferably the polymer has a carbon to hydrogen ratio of not more than 1.1, more preferably not more than 1.0, especially not more than 0.75 and most especially not more than 0.65.
- It is possible for the polyester or polyamide to include one or more aromatic moieties in addition to its aliphatic moieties, and indeed a number of preferred polymers do so. However the polymer should have sufficient aliphatic nature that the C:H ratio is not too high. Preferred polyamides include the nylons, e.g. nylon 46, nylon 6, nylon 7, nylon 66, nylon 610, nylon 611, nylon 612, nylon 11, nylon 12 and nylon 1212 and aliphatic/aromatic polyamides, e.g. those based on the condensation of an aromatic dicarboxylic acid and an aliphatic diamene such as polyamides based on the condensation of terephthalic acid with trimethylhexamethylene diamine (preferably containing a mixture of 2,2,4-and 2,4,4-trimethylhexamethylene diamine isomers), polyamides formed from the condensation of one or more bisaminomethylnorbornane isomers with one or more aliphatic, cycloaliphatic or aromatic dicarboxylic acids e.g. terephthalic acid and optionally including one or more amino acid or lactam e.g. s-caprolactam comonomers, polyamides based on units derived from laurinlactam, isophthalic acid and bis-(4-amino-3-methylcyclohexyl) methane, polyamides based on the condensation of 2,2-bis-(p-aminocyclohexyl) propane with adipic and azeleic acids, and polyamides based on the condensation of trans cyclohexane-1,4-dicarboxylic acid with the trimethylhexamethylene diamine isomers mentioned above.
- Other preferred aliphatic polymers include those based on polyether and polyamide blocks, especially the so called a "polyether-ester amide block copolymers" of repeating unit:
- Preferably the polyamide sequence is formed from alpha,omega-aminocarboxylic acids, lactams or dia- mine/dicarboxylic acid combinations that include C4 to C14 carbon chains, and the polyoxyalkylene sequence is based on ethylene glycol, propylene glycol and/or tetramethylene glycol, and the polyoxyalkylene sequence constitutes from 5 to 85%, especially from 10 to 50% of the total block copolymer by weight. These polymers and their preparation are described in UK Patent Specifications Nos. 1,473,972, 1,532,930, 1,555,644, 2,005,283Aand 2,011,450A.
- The polyesters that are used in the inner layer preferably include those based on a polyalkylene diol, preferably having a least 3 carbon atoms, or cycloaliphatic diol and an aromatic dicarboxylic acid. Preferred polyesters include polytetramethylene terephthalate, and cycloaliphatic diol terephthalic acid copolymers e.g. copolymers of terephthalate and isophthalate units with 1,4-cyclohexanedimethyloxy units. The polyesters can include polyether esters, for example polyether polyester block copolymers having long chain units of the general formula:
- in which G is a divalent radical remaining after the removal of terminal hydroxyl groups from a polyalkylene oxide) glycol, preferably a poly (C2 to C4 alkylene oxide) having a molecular weight of about 600 to 6000; R is a divalent radical remaining after removal of carboxyl groups from at least one dicarboxylic acid having a molecular weight of less than about 300; and D is a divalent radical remaining after removal of hydroxyl groups from at least one diol having a molecular weight less than 250.
- Preferred examples of such copolyesters are the polyether ester polymers derived from terephthalic acid, polytetramethylene ether glycol and 1,4-butane diol. These are random block copolymers having crystalline hard blocks with the repeating unit:
- If desired the polyamide or polyester may be blended with one or more other polymers. For example polyamides may be used as blends with the polyesters, polyolefins such as polyethylene, ethylene ethyl acrylate copolymers or styrene/diene block copolymers, and the polyesters may be used as blends with ionomers or the above polymers referred to in connection with polyamides.
- The preferred aromatic polymers which are used in this invention are well known to those skilled in the art, and reference may be made for example to U.S. Patents Nos. 3,025,605, 3,306,874, 3,257,357, 3,354,129, 3,441,538, 3,442,538, 3,446,654, 3,658,938, 3,677,921, 3,838,097, 3,847,867, 3,953,400, 3,956,240, 4,107,147, 4,108,837, 4,111,908, 4,175,175, 4,293,670, 4,320,224, and 3,446,654, British Patents Nos. 971,227, 1,369,210 and 1,599,106 and European Patent Applications Nos. 170,065, 124,276 and 178,185. Such polymers include polyketones, polyether ketones, polyether ether ketones, polyether sulphones, polyether ketone/sulphone copolymers, polyether imides and polyphenylene oxides. Blends of different polymers can be used. Preferred aromatic polymers are polymers with a melting or softening point of at least 250°C, particularly at least 300°C and which may be crystalline or amorphous. Softening points of amorphous polymers may conveniently be measured by thermomechanical analysis (TMA), in which case the softening point refers to the temperature at which the probe has reached 60% penetration.
- The polymers may be wholly aromatic or they may include one or more aliphatic moieties.
- In one class of such polymers the polymer comprises, and preferably consists essentially of, units of the formula
wherein Ar represents an unsubstituted or substituted divalent aromatic radical and Q represents -O-, -S-, - S02-, -CO-, -NH-CO- or -COO-, or Ar represents a trivalent radical and Q represents -
- In another class of aromatic polymers the aromatic polymer is a crystalline polyarylene ether comprising recurring units of the formula
- In another class of aromatic polymers, the polymer is a polyether imide or polysulphone imide which comprises recurring units of the formula
-
- R' represents an arylene group.
- Another class of polymers is the polyetherketones that have repeating groups comprising aromatic ether and aromatic ketone groups together with an imide, amide, ester, benzoxazole or benzothiazole group. Examples of such polymers are those having repeating units of the formula:
- Yet another class of aromatic polymer is the polyarylates. Polyarylates that may be used include those that are derived from dihydric phenols and at least one aromatic dicarboxylic acid. Examples of such polymers include those derived from a dihydric phenol of the general formula
- Preferred aromatic polymers consist essentially of repeating units having one of the following formulae
- Other polymers containing aromatic moieties e.g. poly 1,12-dodecamethylene pyromellitimide or 1,13-tri- decamethylene pyromellitimide, as described in U.S. patent No. 3,551,200, may be used.
- Blends of any two or more of the above polymers may be employed as may copolymers based on any two or more of these polymers. In addition, blends of any of these aromatic polymers with aliphatic polymers, e.g. the aliphatic polymers referred to herein may be used.
- Many aromatic polymers that are used in the wire insulation will have a char residue of at least 30%, some polymers having a char residue of at least 40% and even at least 50%. This does not mean to say that a high char value is desired for its own sake, but simply that good mechanical and physical properties of these aromatic polymers including temperature stability and fire retardancy, are usually associated with high char residues. The preferred aromatic polymers will usually have a molar C:H ratio of at least 1.0, preferably at least 1.2, more preferably at least 1.3 and especially at least 1.4. The toughest polymers such as the polyaryl ether ketones, which are associated with high char residues, will have C:H ratios greater than 1.5.
- Although it is possible to employ the aromatic polymer in the form of a blend with one or more aliphatic polymers in addition to, or instead of, any other aromatic polymers for example as described in our copending British applications nos. 8716304 and 8716307 (from which International application nos. W089/00756 and W089/00758 claim priority), the outer layer will usually consist solely of the aromatic polymer as the polymeric component.
- Preferably also, the wire insulation is substantially free of halogens, since the presence of significant quantities of halogens can cause corrosive and toxic gases to be emitted when the wire is subjected to a fire. Preferably the wire insulation contains not more than 10% by weight halogens, more preferably not more than 5% by weight halogens and especially substantially no halogens.
- The wire insulation, or at least the inner layer may be cross-linked, for example, by exposure to high energy radiation.
- Radiation cross-linking may be effected by exposure to high energy irradiation such as an electron beam or gamma-rays. Radiation dosages in the range 20 to 800 kGy, preferably 20 to 500 kGy, e.g. 20 to 200 kGy and particularly 40 to 120 kGy are in general appropriate depending on the characteristics of the polymer in question. For the purposes of promoting cross-linking during irradiation, preferably from 0.2 to 15 weight per cent of a prorad such as a poly-functional vinyl or allyl compound, for example, triallyl cyanurate, triallyl isocyanurate (TAIC), methylene bis acrylamide, metaphenylene diamine bis maleimide or other crosslinking agents, for example as described in U.S. patents Nos. 4,121,001 and 4,176,027, are incorporated into the composition prior to irradiation.
- The insulation may include additional additives, for example reinforcing or non-reinforcing fillers, stabilisers such as ultra-violet stabilisers, antioxidants, acid acceptors and anti-hydrolysis stabilisers, pigments, processing aids such as plasticizers, halogenated or non-halogenated flame retardants e.g. hydrated metal oxides such as alumina trihydrate or magnesium hydroxide, or decabromodiphenyl ether, fungicides and the like.
- In many cases the wire insulation will consist solely of the polyamide/polyester inner layer and the aromatic outer layer. However, if desired one or more other layers may be present. For example an additional inorganic arc-control layer may be provided directly on the conductor, formed for example by deposition of an inorganic material on the conductor. Such a layer would enable the thickness of the inner insulating layer to be reduced. Alternatively or in addition a wet-tracking control layer, which will normally have a low carbonaceous char residue e.g. not more than 15% by weight and which may be formed, for example, from an aliphatic polymer, may be provided on top of the aromatic polymer in order to improve the resistance of the insulation to wet tracking (the phenomenon of wet tracking being described in our British patent application No. 8716304 (International Application W089/00756) mentioned above.
- The wires and cables according to the invention may be formed by conventional techniques. For example the polymers may be blended with any additional components, in a mixer, pelletised, and then extruded onto a wire conductor.
- The wires may be used individually as equipment or "hook-up" wires, or airframe wires, or in bundles and harnesses, both jacketted and unjacketted, and may be used in multiconductor cables. The wires, harnesses or cables may be unscreened or they may be provided with a screen to protect them from electromagnetic interference, as well known in the art. In addition flat cables may be formed using the insulation materials according to the invention, either employing flat conductors or round conductors.
- The invention will now be described by way of example with reference to the accompanying drawings, in which:
- Figure 1 is an isometric view of a wire in accordance with the invention;
- Figure 2 is a schematic view of the test arrangement for wet tracking; and
- Figure 3 is a schematic view of the test arrangement for dry arcing.
- Referring initially to figure 1 of the accompanying drawings, an electrical wire comprises a conductor 11 which may be solid or stranded as shown and is optionally tinned. A 100 micrometre thick inner layer 12 (primary insulation) formed from polybutylene terephthalate or a butylene oxide-butylene terephthalate block copolymer is extruded onto the conductors followed by a 100 micrometre thick layer 13 of polyetherketone, polyether ether ketone or a polyaryletherimide. After the insulating layers have been extruded, or even before layer 13 has been extruded, layer 12 may be crosslinked by irradiating the wire with high energy electrons to a dose of about 120 kGy.
- The following Examples illustrate the invention. In the Examples the following test procedure was used:
- This test is designed to simulate what happens when a fault in a wire bundle causes arcing under dry conditions. Agraphite rod is used to initiate the arc which causes thermal degradation of the insulation. Continuation of the fault current can only occur through the wire bundle under test due to shorting across adjacent phases through a conductive char, or direct conductor-conductor contact such as might occur if the insulation is totally removed by the duration of the arc.
- Figure 1 shows the sample set-up. A
wire bundle 21 is prepared from seven10cm lengths 22 of 22AWG tinned-copper or nickel-plated copper conductor coated with a layer of the wire insulation under test. Thebundle 22 is arranged with six wires around one central wire and held together with tie wraps spaced about 5cm apart. One of the outer wires is notched circumferentially between the tie wraps to expose 0.5mm bare conductor and one end of each wire is stripped to enable connections to be made via insulating crocodile clips. - A
rod 23 is provided which is made of a spectrographically pure graphite, diameter 4.6mm, with an impurity level not more than 20ppm. It is prepared before each test by sharpening one end using a conventional pencil sharpener of European design to give an angle of 10 degrees off vertical with a tip diameter of 0.4±0.1 mm. A100g weight 24 is clamped onto the top of therod 23 to maintain contact during the arc initiation and also acts as a device to limit the depth of penetration of the rod by restricting its downward travel. The rod passes through a PTFE bush which allows it to slide freely up and down. - The arrangement of levers enables precise positioning of the
rod 23 on thewire bundle 21 which is held securely in place by means of asimple clamp 25 made of an electrically insulating resin and mounted on ablock 26 made of the same material. - The power source can be either:
- a) a 3-phase 400Hz 115/200V generator of at least 5kVA capacity
- b) a single phase 50Hz 115V transformer, at least 3kVA capacity
- c) 24V d.c. supplied by two 12V accumulators.
- The fault current is detected by means of current clamps surrounding the connecting leads and the voltage at failure is measured using a 10:1 voltage probe. The transducer signals are fed into a multi-channel digital storage oscilloscope where they can be displayed and manipulated to obtain power curves (voltage x current) and energy (integration of power curve).
- The
wire bundle 21 is positioned in theclamp 25 so that the notched wire is uppermost. Adjacent wires of the bundle are connected to different phases of the supply through 7.5A aircraft type circuit breakers, and the central wire is connected directly to neutral. In the case of single phase or d.c. supplies, alternate wires are connected to neutral or the negative terminal, with the remaining wires, including the central wire, connected through circuit breakers to live or the postive terminal. The carbon rod is also connected to neutral or the negative terminal and positioned so that the point is in contact with the exposed conductor. The gap between the 100g weight and the PTFE bush is adjusted to the diameter of the insulated wire under test using a suitable spacer to limit the penetration of the rod into the sample. A voltage probe is connected across the damaged wire and the rod, and current clamps positioned on each of the three phases, or on the wires connected to the live side of the supply. A protective screen is placed in front of the test set-up and the power switched on. A material is deemed to pass this test if: - a) no circuit breakers come out and the activity is relatively non-eventful, or
- b) there is no further activity on resetting the breakers after a non-eventful test.
- In addition, non-tracking materials will have relatively few spikes in the current trace with a correspondingly low total energy consumed. Tracking materials, on the other hand, show many spikes usually on all three phases, which are accompanied by violent crepitation and large energy consumption.
- The following wire constructions were prepared by extruding onto 22 AWG nickel plated copper wire unless otherwise stated using a 20mm Baughan extruder. In the cases where a blend has been used, it has been prepared using a Baker Perkins twin-screw extruder, and in all cases the inner layer contained 5% TAIC and was crosslinked by high energy electron irradiation to a dose of 120 kGy. Examples 1 to 5 were tested for dry tracking with a 115 V 50 Hz, single phase power source, and the results are given in Table I. Examples 6 to 12 were tested using 115 V, 400 Hz three phase supply, and the results are given in Table II.
- In the Examples the following polymers were used:
-
-
- 100 f..lm of an aromatic-aliphatic polyamide (polymer formed from a mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine and terephthalic acid) was extruded as the inner insulating layer with 100 µm of polyaryletheretherketone as the outer insulating layer.
- 100 µm of a blend of polytetramethylene terephthalate, an ionomer resin (Surlyn 9090 from Dupont) and a crosslinking agent (Diacryl 101) in the ratio of 77.5: 17.5: 5 as the inner insulating layer with 100 um of polyaryletheretherketone as the outer insulating layer.
- 125 um of a blend of polytetramethylene terephthalate and a poly(ether-ester) block copolymer comprising approximately 57% by weight polybutylene terephthalate hard blocks and approximately 43% by weight poly(butylene glycol polyether terephthalate) soft blocks in the ratio of 70:30 as the inner insulating layer with 125 µm of polyaryletheretherketone as the other insulating layer.
- As Example 3 with the exception that the inner insulating layer also contains 20% by weight hydrated zinc borate.
- 250 µm polyaryletheretherketone as a single insulating layer.
- 100 µm of a polyether block amide as the inner layer, and 100 µm of a polyetherimide as the outer layer.
- 100 µm of polyethylene terephthalate as the inner layer and 100 µm of a polyetherimide as the outer layer.
- 100 µm of polyaryletheretherketone as the sole layer.
- 100 µm of polyetherimide as the sole layer.
- 100 µm of an amorphous polyamide based on laurinlactam, isophthalic acid bis-(4-amino-3-methylcyclohexyl) methane, as the inner layer and 100 µm of polyaryletheretherketone as the outer layer.
- 100 µm of polytetramethylene terephthalate as the inner layer and 100 µm of polyaryletheretherketone as the outer layer.
- 100 µm of the same polyamide as in Example 1 for the inner layer, and 100 µm of polyaryletheretherketone as the outer layer.
-
Claims (12)
wherein Ar represents an unsubstituted or substituted divalent aromatic radical and Q represents -O-, -S-, -S02-, -CO-, -NH-CO- or -COO-, or Ar represents a trivalent radical and Q represents
ii) a crystalline polyarylene ether comprising recurring units of the formula: -0-E-O-E'- wherein E is the residue of a dihydric phenol and E' is the residue of an aromatic compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, the E and E' radicals being linked to the -O- radicals through aromatic carbon atoms; or
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88905963T ATE85146T1 (en) | 1987-07-10 | 1988-07-08 | ELECTRIC WIRE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8716306 | 1987-07-10 | ||
GB878716306A GB8716306D0 (en) | 1987-07-10 | 1987-07-10 | Electrical wire |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0366700A1 EP0366700A1 (en) | 1990-05-09 |
EP0366700B1 true EP0366700B1 (en) | 1993-01-27 |
Family
ID=10620456
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88905963A Expired - Lifetime EP0366700B1 (en) | 1987-07-10 | 1988-07-08 | Electrical wire |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0366700B1 (en) |
JP (1) | JP3036753B2 (en) |
AT (1) | ATE85146T1 (en) |
CA (1) | CA1319738C (en) |
DE (1) | DE3877963T2 (en) |
GB (1) | GB8716306D0 (en) |
WO (1) | WO1989000761A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3089170A4 (en) * | 2013-12-26 | 2017-08-16 | Furukawa Electric Co., Ltd. | Multilayer insulated wire, coil and electrical/electronic device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1271797B (en) * | 1994-12-23 | 1997-06-09 | Pirelli Cavi Spa | SELF-EXTINGUISHING AND LOW EMISSION CABLE OF SMOKE AND GAS AND TOXIC AND CORROSIVE AND PROCEDURE FOR ITS PRODUCTION |
WO1993018526A1 (en) * | 1992-03-06 | 1993-09-16 | Raychem Corporation | Dual wall insulation and jacketing |
JPH11176244A (en) * | 1997-10-06 | 1999-07-02 | Furukawa Electric Co Ltd:The | Multi-layer insulated wire and transformer using it |
WO1999030330A1 (en) * | 1997-12-08 | 1999-06-17 | Acome Societe Cooperative De Travailleurs | Electric wire with thin insulation based on polybutyleneterephthalate |
JP2009126986A (en) * | 2007-11-27 | 2009-06-11 | Totoku Electric Co Ltd | High heat-resistant self fusing coating and high heat-resistant self fusing insulated wire |
US8980053B2 (en) | 2012-03-30 | 2015-03-17 | Sabic Innovative Plastics Ip B.V. | Transformer paper and other non-conductive transformer components |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0175419B1 (en) * | 1984-09-18 | 1989-01-04 | Nkf Kabel B.V. | Signal transmission cable |
-
1987
- 1987-07-10 GB GB878716306A patent/GB8716306D0/en active Pending
-
1988
- 1988-07-08 JP JP63505733A patent/JP3036753B2/en not_active Expired - Fee Related
- 1988-07-08 AT AT88905963T patent/ATE85146T1/en not_active IP Right Cessation
- 1988-07-08 CA CA000571502A patent/CA1319738C/en not_active Expired - Lifetime
- 1988-07-08 EP EP88905963A patent/EP0366700B1/en not_active Expired - Lifetime
- 1988-07-08 WO PCT/GB1988/000547 patent/WO1989000761A1/en active IP Right Grant
- 1988-07-08 DE DE8888905963T patent/DE3877963T2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3089170A4 (en) * | 2013-12-26 | 2017-08-16 | Furukawa Electric Co., Ltd. | Multilayer insulated wire, coil and electrical/electronic device |
US10032540B2 (en) | 2013-12-26 | 2018-07-24 | Furukawa Electric Co., Ltd. | Multilayer insulated wire, coil, and electrical/electronic equipment |
Also Published As
Publication number | Publication date |
---|---|
DE3877963T2 (en) | 1993-05-13 |
GB8716306D0 (en) | 1987-08-19 |
DE3877963D1 (en) | 1993-03-11 |
WO1989000761A1 (en) | 1989-01-26 |
EP0366700A1 (en) | 1990-05-09 |
ATE85146T1 (en) | 1993-02-15 |
JP3036753B2 (en) | 2000-04-24 |
CA1319738C (en) | 1993-06-29 |
JPH02504201A (en) | 1990-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0360836B1 (en) | Electrical wire | |
EP0224281B1 (en) | Flame retarded cladding | |
EP0414748B1 (en) | Polymeric composition | |
WO1989000756A1 (en) | Electrical wire and cable | |
EP0366700B1 (en) | Electrical wire | |
EP0371048B1 (en) | Electrical wire | |
CA1214528A (en) | Electrical insulation with improved flexibility and preferably with low smoke evolution characteristics | |
CA1307837C (en) | Dual wall wire having polyester fluoropolymer insulation | |
WO1993007627A1 (en) | Electrical wire | |
GB2170646A (en) | Flame retardant cable | |
AU606731B2 (en) | Electrical wire with polyamide/fluoropolymer insulation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19891227 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17Q | First examination report despatched |
Effective date: 19920318 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19930127 Ref country code: NL Effective date: 19930127 Ref country code: AT Effective date: 19930127 |
|
REF | Corresponds to: |
Ref document number: 85146 Country of ref document: AT Date of ref document: 19930215 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3877963 Country of ref document: DE Date of ref document: 19930311 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed | ||
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060717 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20060726 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20060727 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20060731 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20060828 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20060831 Year of fee payment: 19 |
|
BERE | Be: lapsed |
Owner name: *RAYCHEM LTD Effective date: 20070731 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20070708 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070731 Ref country code: DE Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 20080103 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070708 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20080331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070708 |