TWI570751B - 防火且防水之電纜 - Google Patents
防火且防水之電纜 Download PDFInfo
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- TWI570751B TWI570751B TW103109481A TW103109481A TWI570751B TW I570751 B TWI570751 B TW I570751B TW 103109481 A TW103109481 A TW 103109481A TW 103109481 A TW103109481 A TW 103109481A TW I570751 B TWI570751 B TW I570751B
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- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- H01B3/44—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 vinyl resins; acrylic resins
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- 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
- H01B3/44—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 vinyl resins; acrylic resins
- H01B3/441—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 vinyl resins; acrylic resins from alkenes
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- 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
- H01B3/44—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 vinyl resins; acrylic resins
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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Description
本申請案係2012年12月13日申請之美國專利申請案第13/713,535號之部分接續案(CIP),其係以引用方式併入本文中。
本發明係關於用於電線及電纜之防火且防水的電纜包覆組合物(絕緣件或夾套)。重要的是,該組合物不含大量鉛、鹵素及/或銻。
過去已利用聚合材料作為電纜之電絕緣材料。在需要電纜之長期性能之服務或產品中,該等聚合材料除了具有適宜介電性質以外必須具有耐久性。舉例而言,出於安全及經濟需要及實用性,用於構建電線、電動機或機械動力線或地下輸電電纜之聚合絕緣件必須具有耐久性。
最常見聚合絕緣體係由聚乙烯均聚物或乙烯-丙烯彈性體製成,或者稱為乙烯-丙烯橡膠(EPR)及/或乙烯-丙烯-二烯三元共聚物(EPDM)。在所申請的EPR或EPDM絕緣件中已使用鉛(例如氧化鉛)作為水樹抑制劑及離子清除劑;然而,鉛有毒。
亦期望同時具有防火性質及防潮性質之經塗佈電纜。在絕緣件中使用典型阻燃劑。鹵化添加劑(基於氟、氯或溴之化合物)或含鹵素聚合物(例如聚氯乙烯)能使形成絕緣件之聚合物具有防火性質,但缺點在於,鹵化化合物之分解產物具有腐蝕性且有害。因此,不推薦使用鹵素,尤其不推薦在封閉場所使用。
或者,或與鹵素組合,可將阻焰劑添加劑(例如氧化銻)添加至適當絕緣聚合物中。
因此,業內仍需要環境友好之防潮且防火之無鉛、無鹵素且無銻之電纜絕緣件。
本發明之目標係提供可用作電纜包覆材料(絕緣件或夾套)之無鹵素、無鉛且無銻之組合物,其係阻焰劑(UL 1685(2007)電纜托盤燃燒測試)且具有極佳電、機械及防水性質(例如UL 44(2010)長期絕緣電阻(LTIR))。
本發明提供用於電纜之電纜包覆組合物(絕緣件或夾套),其含有(a)聚烯烴;(b)馬來酸酐改質之聚烯烴;(c)丁二烯-苯乙烯共聚物;(d)無鹵素阻焰劑;及(e)矽烷化合物。有利地,該組合物無鉛、無鹵素且無銻。如本文所用的片語「無鉛」或「無大量鉛」或諸如此類係指鉛含量基於總組合物低於1000百萬分率(ppm),較佳低於300ppm,最佳使用當前分析技術不可檢測。如本文所用片語「無鹵素」或「無大量鹵素」或諸如此類係指鹵素含量低於1000ppm,較佳低於300ppm,最佳使用當前分析技術不可檢測。如本文所用片語「無銻」或「無大量銻」或諸如此類係指銻含量低於1000ppm,較佳低於300ppm,最佳使用當前分析技術不可檢測。
本發明亦提供含有由至少一個絕緣層包圍之電導體之電纜。絕緣件含有(a)聚烯烴;(b)馬來酸酐改質之聚烯烴;(c)丁二烯-苯乙烯共聚物;(d)無鹵素阻焰劑;及(e)矽烷化合物。較佳地,僅用單一絕緣層包覆導體,不需要多個層。若1/0 AWG電纜之絕緣件厚度大於約75-100密耳,則該電纜較佳在電導體與絕緣件之間含有阻燃帶。
本發明亦提供藉由在電纜上擠出至少一個絕緣層來製備無鉛、無鹵素且無銻電纜之方法。絕緣件係由含有以下物質之聚合物化合物
製成:(a)聚烯烴;(b)馬來酸酐改質之聚烯烴;(c)丁二烯-苯乙烯共聚物;(d)無鹵素阻焰劑;及(e)矽烷化合物。若1/0 AWG電纜之絕緣層之總厚度大於約75-100密耳,則該方法進一步預期在導體上纏繞阻燃帶,之後在纏繞帶上擠出至少一個絕緣件。該帶之添加容許含有厚絕緣件之電纜在90℃下除了UL 44(2010)LTIR以外亦符合UL 1685(2007)。
100‧‧‧電纜
102‧‧‧導體
104‧‧‧阻燃分離帶
106‧‧‧絕緣件
圖1係本發明電纜之截面圖,其經設計以符合UL 1685(2007)且具有厚絕緣件。
本發明組合物含有聚烯烴基礎聚合物及添加劑。如本文所用聚烯烴係自具有通式CnH2n之烯烴產生之聚合物。
在上文廣義定義內,適合於本發明之聚烯烴之非限制性實例包括聚乙烯(包括低密度(LDPE)、高密度、高分子量(HDPE)、超高分子量(UHDPE)、線性低密度(LLDPE)、極低密度等)、馬來酸化聚丙烯、聚丙烯、聚丁烯、聚己烯、聚辛烯及其共聚物,以及乙烯-乙酸乙烯酯(EVA)共聚物及其混合物、摻合物或合金。
茂金屬催化之烯烴共聚物可在本發明之聚合物合金中構成另一聚合物。合金中包括彼等共聚物以改變聚烯烴之模數且以其他方式有助於聚烯烴在製造期間之可處理性。
該等茂金屬催化之烯烴共聚物為業內所熟知,例如揭示於美國專利第6,451,894號、第6,376,623號及第6,329,454號中。該等共聚物可自多個商業來源獲得,尤其係ExxonMobil及Dow Elastomers。
業內熟知,茂金屬催化可產生極精確之聚合結構。在用於共聚之烯烴單體之可能性內,較佳使用乙烯及具有3至18個碳原子之第二烯烴單體。在共聚單體之選擇中,辛烯由於所得共聚物之熔流性質之
可能的變化而較佳。
用於本發明電纜之包覆組合物(例如絕緣件或夾套)中之基礎聚合物亦可選自由以下組成之群:由與至少一種共聚單體聚合之乙烯組成之聚合物,該共聚單體選自由C3至C20 α-烯烴及C3至C20多烯組成之群。一般而言,適用於本發明之α-烯烴含有在約3至約20個範圍內之碳原子。較佳地,α-烯烴含有在約3至約16個範圍內之碳原子,最佳在約3至約8個範圍內之碳原子。該等α-烯烴之說明性非限制性實例係丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯及1-十二烯。
聚合物可包括乙烯/α-烯烴共聚物或乙烯/α-烯烴/二烯三元聚合物。用於本發明中之多烯一般具有約3至約20個碳原子。多烯具有在約4至約20個範圍內之碳原子,最佳在約4至約15個範圍內之碳原子。多烯可為二烯,其可為直鏈、具支鏈或環狀烴二烯。最佳地,二烯係非共軛二烯。適宜二烯之實例係直鏈非環狀二烯,例如:1,3-丁二烯、1,4-己二烯及1,6-辛二烯;具支鏈非環狀二烯例如:5-甲基-1,4-己二烯、3,7-二甲基-1,6-辛二烯、3,7-二甲基-1,7-辛二烯及二氫月桂烯與二氫羅勒烯之混合異構物;單環脂環族二烯,例如:1,3-環戊二烯、1,4-環己二烯、1,5-環辛二烯及1,5-環十二碳二烯;及多環脂環族稠合及橋接環二烯,例如:四氫茚、甲基四氫茚、二環戊二烯、雙環-(2,2,1)-庚-2-5-二烯;烯基、亞烷基、環烯基及環亞烷基降莰烯,例如:5-亞甲基-2降莰烯(MNB)、5-丙烯基-2-降莰烯、5-異亞丙基-2-降莰烯、5-(4-環戊烯基)-2-降莰烯、5-環亞己基-2-降莰烯及降莰烯。在通常用於製備EPR之二烯中,尤佳二烯係1,4-己二烯、5-亞乙基-2-降莰烯、5-亞乙烯基-2-降莰烯、5-亞甲基-2-降莰烯及二環戊二烯。
作為基礎聚合物組合物中之另一聚合物,可使用具有上文所述任一聚烯烴或聚烯烴共聚物之結構式之非茂金屬基礎聚合物。乙烯-丙烯橡膠(EPR)、聚乙烯、聚丙烯或乙酸乙烯酯含量在約10%至約60%
範圍內之乙烯乙酸乙烯酯皆可與其他聚合物組合用於基礎聚合物中,以給予基礎聚合物其他期望性質。然而,如上文所陳述,諸如原材料之成本及可用性以及終端使用者在某些環境中之要求可指定某些組合物,或使某些在其他情況下可能並非較佳之實施例在某些情況下較佳。
較佳基礎聚合物係茂金屬催化之烯烴。基礎聚合物較佳係以組合物之約20重量%至約50重量%存在,更佳為約20重量%至約40重量%,且最佳為約25重量%至約35重量%。
本發明組合物亦包括馬來酸酐改質之聚烯烴(MAMP)。上文所提及之用於基礎聚合物之任一聚烯烴皆適合於此處之改質。馬來酸酐改質之聚乙烯較佳用於組合物中,且可以Lotader、Fusabond、Orevac或Elvaloy購得。MAMP較佳係以組合物之約1重量%至約15重量%存在,更佳為約1重量%至約5重量%,且最佳為約1.5重量%至約4重量%。
本發明組合物亦包括丁二烯-苯乙烯共聚物,其較佳以組合物之約0.5重量%至約20重量%存在,更佳為約0.5重量%至約8重量%,且最佳為約1重量%至約3重量%。共聚物之苯乙烯含量較佳為約20-30重量%。在一個實施例中,苯乙烯共聚物可包括(例如)由苯乙烯及丁二烯製成之嵌段共聚物。在另一實施例中,苯乙烯共聚物含有苯乙烯及丁二烯之隨機排列。在較佳實施例中,苯乙烯共聚物係苯乙烯及乙烯之隨機排列。丁二烯-苯乙烯共聚物可以(例如)Ricon、Solprene、Synpol、Stereon或Pliolite購得。
本發明組合物亦包括無鹵素阻焰劑。無鹵素阻焰劑可包括(例如)無機阻焰劑,例如氫氧化鋁及氫氧化鎂;及/或含磷阻焰劑,例如磷酸化合物、多磷酸化合物及紅磷化合物。阻焰劑較佳以組合物之約30重量%至約75重量%存在,更佳為約40重量%至約65重量%,且最佳
為約45重量%至約60重量%。較佳阻焰劑係氫氧化鎂,且更佳為未經處理之低離子含量氫氧化鎂。氫氧化鎂之平均粒徑較佳為約0.5至3.0微米,更佳為約0.8至2.0微米,最佳為約0.8至1.2微米。適合於本發明之市售氫氧化鎂包括Zerogen、Magnifin、ICL FR20及Kisuma。
本發明組合物亦包括矽烷化合物,較佳係有機矽烷。矽烷化合物之實例可包括(但不限於)γ-甲基丙烯醯氧基丙基三甲氧基矽烷、甲基三乙氧基矽烷、甲基叁(2-甲氧基乙氧基)矽烷、二甲基二乙氧基矽烷、乙烯基叁(2-甲氧基乙氧基)矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、辛基三乙氧基矽烷、異丁基三乙氧基矽烷、異丁基三甲氧基矽烷、丙基三乙氧基矽烷及其混合物或聚合物。矽烷化合物較佳係以組合物之約0.2重量%至約5重量%存在,更佳為約0.3重量%至約3重量%,且最佳為約0.5重量%至約2重量%。較佳矽烷化合物係乙烯基三乙氧基矽烷與丙基三乙氧基矽烷之聚合物。
本發明組合物亦可包括交聯劑。較佳使用過氧化物作為交聯劑且其可為(但不限於)α,α'-雙(第三丁基過氧基)二異丙基苯、二(第三丁基過氧基異丙基)苯及二枯基過氧化物、第三丁基枯基過氧化物。可使用其他固化方法來代替過氧化物或取代過氧化物,包括電子束照射。交聯劑較佳係以組合物之約0.1重量%至約5重量%存在,更佳為約0.3重量%至約2重量%,且最佳為約0.3重量%至約1.0重量%。較佳交聯劑係1,1-二甲基乙基1-甲基-1-苯基乙基過氧化物、雙(1-甲基-1-苯基乙基)過氧化物及[1,3(或1,4)-伸苯基雙(1-甲基亞乙基)]雙[(1,1-二甲基乙基)過氧化物之摻合物。
本發明組合物亦可包括在不影響本發明目標之範圍內之一般用於絕緣電線或電纜之其他添加劑,例如填充劑、抗氧化劑、處理助劑、著色劑及穩定劑。
填充劑可為(例如)炭黑、黏土(較佳係經處理或未經處理之無水
矽酸鋁)、氧化鋅、氧化錫、氧化鎂、氧化鉬、三氧化銻、二氧化矽(較佳係沈澱二氧化矽或親水發煙二氧化矽)、滑石粉。填充劑較佳係以組合物之約0至約40重量%存在,更佳為約0至約30重量%,且最佳為約5重量%至約15重量%。較佳填充劑係經矽烷處理之矽酸鋁(黏土),其係作為Translink、Polyfil或Polarite購得。
抗氧化劑可包括(例如)胺-抗氧化劑,例如4,4'-二辛基二苯胺、N,N'-二苯基-對伸苯基二胺及2,2,4-三甲基-1,2-二氫喹啉之聚合物;酚類抗氧化劑,例如硫代二乙烯雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、4,4'-硫代雙(2-第三丁基-5-甲基苯酚)、2,2'-硫代雙(4-甲基-6-第三丁基-苯酚)、苯丙酸、3,5雙(1,1二甲基乙基)4-羥基苯丙酸、3,5-雙(1,1-二甲基乙基)-4-羥基-C13-15具支鏈及直鏈烷基酯、3,5-二第三丁基-4羥基氫桂皮酸C7-9-具支鏈烷基酯、2,4-二甲基-6-第三丁基苯酚四{亞甲基3-(3',5'-二第三丁基-4'-羥基苯酚)丙酸酯}甲烷或四{亞甲基3-(3',5'-二第三丁基-4'-氫桂皮酸酯}甲烷、1,1,3叁(2-甲基-4羥基5丁基苯基)丁烷、2,5,二第三戊基氫醌、1,3,5-三甲基2,4,6叁(3,5二第三丁基4羥基苄基)苯、1,3,5叁(3,5二第三丁基4羥基苄基)異氰脲酸酯、2,2亞甲基-雙-(4-甲基-6-第三丁基-苯酚)、6,6'-二第三丁基-2,2'-硫代二對甲酚或2,2'-硫代雙(4-甲基-6-第三丁基苯酚)、2,2乙烯雙(4,6-二第三丁基苯酚)、三乙二醇雙{3-(3-第三丁基-4-羥基-5甲基苯基)丙酸酯}、1,3,5叁(4第三丁基3羥基-2,6-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)三酮、2,2亞甲基雙{6-(1-甲基環己基)-對甲酚};及/或含硫抗氧化劑,例如雙(2-甲基-4-(3-正烷基硫代丙醯氧基)-5-第三丁基苯基)硫化物、2-巰基苯并咪唑及其鋅鹽及新戊四醇-四(3-月桂基-硫代丙酸酯)。抗氧化劑較佳係以組合物之約0.1重量%至約10重量%存在,更佳為約0.2重量%至約5重量%,且最佳為約0.5重量%至約2重量%。較佳抗氧化劑係2-巰基苯并咪唑鋅鹽及/或聚合2,2,4-三甲基-1,2-二氫喹啉之摻
合物。
視情況使用處理助劑來改良聚合物之可處理性。處理助劑在聚合物載劑內形成微觀分散相。在處理期間,所施加剪切分離處理助劑相與載劑聚合物相。然後處理助劑移動至模具壁,逐漸形成連續塗層以減小擠出機之背壓,從而減小擠出期間之摩擦。處理助劑一般係潤滑劑,例如(但不限於)硬脂酸、聚矽氧、抗靜電胺、有機胺、乙醇醯胺、單-及二甘油酯脂肪胺、乙氧基化脂肪胺、脂肪酸、硬脂酸鋅、硬脂酸、棕櫚酸、硬脂酸鈣、硫酸鋅、寡聚烯烴油及其組合。處理助劑較佳係以組合物之低於約10重量%存在,更佳低於約5重量%,且最佳低於約1重量%。較佳處理助劑係脂肪酸之摻合物,其可以Struktol、Ultraflow、Moldwiz或Aflux購得。
本發明組合物可藉由使用習用撕捏設備(例如橡膠磨機、Brabender混合器、Banbury混合器、Buss-Ko捏合機、Farrel連續混合器或雙螺桿連續混合器)摻和各組份來製備。添加劑在被添加至基礎聚烯烴聚合物中之前較佳經預混合。混合時間應足以獲得均勻摻合物。通常在將本發明中所用組合物之所有組份引入擠出裝置中之前將其摻和或複合在一起,自該擠出裝置將該等組份擠出至電導體上。
在將組合物之各個組份均勻混合並摻和在一起後,對其進行進一步處理以製造本發明電纜。用於製造聚合物電纜絕緣件或電纜夾套之先前技術方法為人所熟知,且本發明電纜之製造一般可藉由多種擠出方法中之任一種來完成。
在典型擠出方法中,牽拉欲塗佈之視情況經加熱之導電核心經過經加熱擠出模具(一般係十字頭模具),在該模具中將熔融聚合物層施加至導電核心上。在離開模具後,若聚合物經調整為熱固性組合物,則可將具有所施加聚合物層之導電核心通過經加熱硫化工段或連續硫化工段,之後通過冷卻工段(一般係延長冷卻浴)以冷卻。可藉由
連續擠出步驟(其中每一步驟中添加另一層)或用適當類型之模具施加多個聚合物層,多個聚合物層可同時施加。
本發明導體一般可包含任何適宜導電材料,但一般利用導電金屬。較佳地,所利用金屬係銅或鋁。
通常,在使用本發明作為絕緣件時,對於1/0 AWG電纜,絕緣件之厚度(可在多個層上)一般可為約45密耳至約80密耳。然而,端視電纜大小,在某些實施例中,例如對於較大電纜大小,厚度可大於約80密耳,較佳大於約90密耳,最佳為100密耳或更大。對於較小電纜大小,厚度可低於45密耳。在大於約75-100密耳(較佳大於約75密耳,更佳大於約85密耳,最佳大於約100密耳)下,尤其對於1/0 AWG電線,電纜構造必須經修改以符合UL 1685(2007)。因此,在如圖1中所繪示之本發明實施例中,電纜100含有經阻燃分離帶104纏繞之導體102。然後用至少一層由本發明組合物製成之絕緣件106包覆分離帶104。絕緣件之厚度較佳大於約75密耳,較佳大於約85密耳,更佳大於約100密耳(對於1/0 AWG電線)。絕緣件可為單一層或多個層。如圖1中圖解說明,亦可使用一層以上的絕緣件,較佳在一層上擠出另一層。在使用多個層時,絕緣層之總厚度較佳大於約75密耳,較佳大於約85密耳,更佳大於約100密耳。該帶在對包覆層之電或機械性質無不良影響之情況下改良電纜之防火性。在期望電纜包覆過厚且對電纜之防火特徵造成不良影響時,阻燃帶減輕該不良效應並容許電纜符合對耐火電纜之標準,且對包覆層之電或機械性質不造成不良影響。
阻燃分離帶較佳係含有納入其中之無鹵素阻燃劑之纖維帶。纖維帶較佳由編織成織物且厚度小於約10密耳、較佳約3-8密耳、最佳約5密耳之玻璃纖維材料來構築。重要的是,在保持電纜無鉛、無鹵素且無銻時,該帶必須如上文針對「無鉛」、「無鹵素」及「無銻」所定義不含具有大量鉛、鹵素或銻之成份。
浸漬於該帶中之阻燃劑可為上文針對絕緣層所揭示之任一阻燃劑,且氫氧化鎂較佳。該帶較佳含有約50%至約90%(以帶之重量計)、較佳約60%至約80%、更佳約72%至約77%之阻燃劑。可用於本發明之市售帶係POWERLINE®布帶NETTAPE® NTS185(Neptco公司,Pawtucket,RI)。
可將阻燃帶圍繞導體螺旋纏繞;然而,其亦可圍繞導體縱向安置。螺旋纏繞較佳,此乃因其可經調整用於現有製程。
儘管上文說明及圖式已顯示如置於導體與包覆層之間之阻燃帶,但可將該帶置於電纜上之其他位置,例如在包覆層(絕緣件或夾套)上、在包覆層之間(若電纜使用多層包覆)及在多個絕緣導體上。
相信熟習此項技術者不經進一步說明即可使用前文說明及下文闡釋性實例來製備及利用本發明化合物並實踐所主張方法。提供以下實例以闡釋本發明。應理解,本發明並不限於實例中闡述之特定條件或細節。
根據本發明製備若干種組合物。彼等組合物顯示於表1中且命名為IA、IB、IC及ID。
* 密度:0.93g/cm3,熔流速率(190℃/2.16kg):1.75g/10min.;**密度:0.922g/cm3,熔流速率(190℃/2.16kg):6.7g/10min。
表2顯示組合物IA至ID之物理及電性質。抗拉強度及伸長率係根據ASTM D412(2010)或D638(2010)使用Zwick通用測試機或Instron測試儀來量測。在90℃下之長期絕緣電阻(LTIR)係根據UL 44(2010)來量測。在90℃下之相對電容率/電容增加係根據UL 44(2010)來測試。
選擇與IB相同(但過氧化物增加至2.3重量份數)之組合物用於UL耐火測試。製備兩個具有80密耳厚度之該絕緣件組合物之電纜樣品(1/0 AWG),且根據UL 1685(2007)來測試。測試結果歸納於表3中。
製備如下兩種類型之電纜:
1)電纜A:用5密耳Mylar分離帶纏繞1/0 AWG銅導體(19股,鍍錫)。在Mylar帶上擠出兩層絕緣件。內層絕緣件厚度為55密耳,而外層絕緣件厚度為45密耳。
2)電纜B:與構造A相同,但用POWERLINE®布帶NEPTAPE® NTS185替代Mylar帶。
兩個絕緣層相同且含有與表1中IB相同之成份(但過氧化物增加至2.3重量份數)。
電纜A與B二者皆係根據UL 1685(2007)來測試。測試結果歸納於表4中。
儘管本文已明確闡述本發明的某些目前較佳的實施例,但本發明所屬領域技術人員將瞭解,可在不背離本發明的精神及範圍之情形下對本文顯示並闡述之各個實施例作出改變及修改。因此,本發明意欲僅受限至隨附申請專利範圍及適用法規要求之程度。
100‧‧‧電纜
102‧‧‧導體
104‧‧‧阻燃分離帶
106‧‧‧絕緣件
Claims (19)
- 一種電纜,其包含導體、阻燃帶及厚度大於約75密耳之絕緣件,該絕緣件係由無鉛、無鹵素且無銻之組合物製成,該組合物包含a)聚烯烴;b)馬來酸酐改質之聚烯烴;c)丁二烯-苯乙烯共聚物;d)無鹵素阻焰劑;及e)矽烷化合物;其中該絕緣件符合UL 44 LTIR在90℃下之要求且該電纜符合UL 1685之防火要求。
- 如請求項1之電纜,其中組份a)係以該組合物之約20重量%至約50重量%存在,組份b)係以該組合物之約1重量%至約15重量%存在,組份c)係以該組合物之約0.5重量%至約20重量%存在,組份d)係以該組合物之約30重量%至約75重量%存在,或組份e)係以該組合物之約0.2重量%至約5重量%存在。
- 如請求項1之電纜,其中組份a)係乙烯丁烯,組份b)係馬來酸酐改質之聚乙烯,組份c)之苯乙烯含量為約20重量%至30重量%,組份d)係氫氧化鎂,或組份e)係乙烯基三乙氧基矽烷及丙基三乙氧基矽烷之聚合物。
- 如請求項1之電纜,其進一步包含交聯劑、填充劑、抗氧化劑及處理助劑之一或多者。
- 如請求項4之電纜,其中該交聯劑係以該組合物之約0.1重量%至約5重量%存在。
- 如請求項4之電纜,其中該填充劑係以該組合物之小於約40重量 %存在。
- 如請求項4之電纜,其中該抗氧化劑係以該組合物之約0.1重量%至約10重量%存在。
- 如請求項4之電纜,其中該處理助劑係以該組合物之小於約10重量%存在。
- 如請求項4之電纜,其中該交聯劑係過氧化物,該填充劑係矽烷處理之矽酸鋁,該抗氧化劑係2-巰基苯并咪唑鋅鹽與2,2,4-三甲基-1,2-二氫喹啉聚合物之組合,或該處理助劑係脂肪酸酯。
- 如請求項1之電纜,其中該阻燃帶係由經無鉛、無鹵素且無銻之阻燃劑浸漬之編織玻璃纖維製成。
- 如請求項1之電纜,其中該阻燃帶之厚度小於約10密耳。
- 如請求項1之電纜,其中該絕緣件包含兩層。
- 一種用於製備電纜之方法,其包含:a)用阻燃帶纏繞導體;及b)在該阻燃帶上擠出絕緣件,其中該絕緣件之厚度大於約75密耳且包含:i)聚烯烴;ii)馬來酸酐改質之聚烯烴;iii)丁二烯-苯乙烯共聚物;iv)無鹵素阻焰劑;及v)矽烷化合物;其中該絕緣件符合UL 44 LTIR在90℃下之要求且該電纜符合UL 1685之防火要求。
- 如請求項13之方法,其中該阻燃帶係由經無鉛、無鹵素且無銻之阻燃劑浸漬之編織玻璃纖維製成。
- 如請求項13之方法,其中該阻燃帶之厚度小於約10密耳。
- 如請求項13之方法,其中該絕緣件包含兩層。
- 如請求項13之方法,其中組份i)係以該組合物之約20重量%至約50重量%存在,組份ii)係以該組合物之約1重量%至約15重量%存在,組份iii)係以該組合物之約0.5重量%至約20重量%存在,組份iv)係以該組合物之約30重量%至約75重量%存在,或組份v)係以該組合物之約0.2重量%至約5重量%存在。
- 如請求項13之方法,其中組份i)係乙烯丁烯,組份ii)係馬來酸酐改質之聚乙烯,組份iii)之苯乙烯含量為約20重量%至30重量%,組份iv)係氫氧化鎂,或組份v)係乙烯基三乙氧基矽烷及丙基三乙氧基矽烷之聚合物。
- 如請求項13之方法,其中該絕緣件進一步包含交聯劑、填充劑、抗氧化劑及處理助劑之一或多者。
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| US13/837,602 US9087629B2 (en) | 2012-12-13 | 2013-03-15 | Fire and water resistant cable |
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| CN108976573A (zh) * | 2018-05-18 | 2018-12-11 | 杭州高新橡塑材料股份有限公司 | 光伏电缆用辐照交联无卤低烟护套料 |
| KR20240042038A (ko) * | 2021-08-11 | 2024-04-01 | 다우 글로벌 테크놀로지스 엘엘씨 | 난연성 중합체 조성물 |
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| JP2002179857A (ja) * | 2000-12-12 | 2002-06-26 | Sumitomo Wiring Syst Ltd | 難燃性樹脂組成物及び被覆電線 |
| CN1625786A (zh) * | 2002-04-29 | 2005-06-08 | 皮雷利&C.有限公司 | 耐火电缆 |
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| JP2003062937A (ja) * | 2001-08-27 | 2003-03-05 | Fujikura Ltd | ノンハロゲン難燃テープ及びこれを用いたフラットケーブル |
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| EP2424940B1 (en) * | 2009-04-29 | 2016-03-09 | PolyOne Corporation | Flame retardant thermoplastic elastomers |
| CN101987902B (zh) * | 2009-07-31 | 2013-01-02 | 索肯(上海)科技有限公司 | 无卤热塑性弹性体及制造方法和使用其的环保电线电缆 |
| CN101914236B (zh) * | 2010-08-19 | 2012-07-11 | 王进 | 一种辐照交联无卤高阻燃电缆料及其制备方法 |
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| US9115274B2 (en) * | 2012-12-13 | 2015-08-25 | General Cable Technologies Corporation | Fire and water resistant cable cover |
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| JP2002179857A (ja) * | 2000-12-12 | 2002-06-26 | Sumitomo Wiring Syst Ltd | 難燃性樹脂組成物及び被覆電線 |
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| CA2902218C (en) | 2020-03-31 |
| AR097230A1 (es) | 2016-03-02 |
| ES2658041T3 (es) | 2018-03-08 |
| MX2015012368A (es) | 2016-02-03 |
| WO2014151297A1 (en) | 2014-09-25 |
| CA2902218A1 (en) | 2014-09-25 |
| BR112015023336A2 (pt) | 2017-07-18 |
| EP2973609A1 (en) | 2016-01-20 |
| EP2973609A4 (en) | 2016-11-02 |
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| EP2973609B1 (en) | 2017-11-01 |
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