TW200407574A - Polymeric optical conductors - Google Patents
Polymeric optical conductors Download PDFInfo
- Publication number
- TW200407574A TW200407574A TW092117253A TW92117253A TW200407574A TW 200407574 A TW200407574 A TW 200407574A TW 092117253 A TW092117253 A TW 092117253A TW 92117253 A TW92117253 A TW 92117253A TW 200407574 A TW200407574 A TW 200407574A
- Authority
- TW
- Taiwan
- Prior art keywords
- molding composition
- weight
- polyamide
- outer layer
- fiber
- Prior art date
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- 230000003287 optical effect Effects 0.000 title claims abstract description 22
- 239000004020 conductor Substances 0.000 title claims description 5
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 46
- 239000004952 Polyamide Substances 0.000 claims abstract description 43
- 229920002647 polyamide Polymers 0.000 claims abstract description 43
- 238000000465 moulding Methods 0.000 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920002614 Polyether block amide Polymers 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
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- 239000000853 adhesive Substances 0.000 claims description 2
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- 239000004615 ingredient Substances 0.000 claims 1
- 239000013307 optical fiber Substances 0.000 claims 1
- 238000005253 cladding Methods 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 44
- 239000011257 shell material Substances 0.000 description 31
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- 239000013309 porous organic framework Substances 0.000 description 16
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- -1 p-aminocyclohexyl Chemical group 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
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- 238000001125 extrusion Methods 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
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- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
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- WSTNFGAKGUERTC-UHFFFAOYSA-N n-ethylhexan-1-amine Chemical compound CCCCCCNCC WSTNFGAKGUERTC-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- CQBIFASRYMRWLF-UHFFFAOYSA-N oxidosulfanium Chemical compound [SH2]=O CQBIFASRYMRWLF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003141 primary amines Chemical group 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4429—Means specially adapted for strengthening or protecting the cables
- G02B6/443—Protective covering
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/045—Light guides
- G02B1/048—Light guides characterised by the cladding material
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4429—Means specially adapted for strengthening or protecting the cables
- G02B6/4436—Heat resistant
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Description
200407574 玖、發明說明: (一)發明所屬之技術領域 本發明係關於一種光纜,其由纖維核、纖 地粘著性之保護性聚醯胺層、及外層組成。 (—)先前技術 聚合物光纖(以下簡稱爲POFs)用於電訊 學傳輸組件,其提供抗破壞強度及操作簡單性 器與接收器間之距離僅數公尺至最大約1 5 0公 在交通工程/車輛建構(機動車輛、飛機、船隻 輸及信號傳輸)、照明(可變交通信號)、自; 機械控制)、及感應器技術(例如,參見D r a h t ,第1 87 -190頁)越來越重要。 作爲資料傳輸或信號傳輸用之P0F由以下 由聚甲基丙烯酸甲酯(PMMA;折射率ηΡΜΜΑ=ΐ.49 維核、及同心地被覆纖維核之單或多層纖維殻 之殼材料爲氟化聚合物,其折射率在1 . 3 5至1 。此P0F之光學衰減一般爲130至150 db/公里 米),及最小彎曲半徑爲約5至1 0毫米。 爲了保護敏感之P〇F不受機械、熱與化學 有作爲保護性被覆之聚合物鞘,而且在適當之 可具有多層結構(W0 9 9 / 1 2063專利)。視應用 而定,例如,藉擠製器應用之聚合物鞘可由聚 聚氯乙烯(PVC)、乙烯—乙酸乙烯酯(EVA)、或 維殼、堅固 領域作爲光 ’不論發送 之。POFs亦 等之資料傳 動化技術( 46(1995)4 組成:經常 )製造之纖 。主要使用 .4 2之範圍 (λ = 6 5 0 奈 影響,其具 處,此鞘亦 或應用領域 乙烯(ΡΕ)、 聚醯胺(ΡΑ) 200407574 組成。 在汽車建構領域’使用聚醯胺作爲保護性被覆材料, 因爲其就機械強度(主要爲張力強度與抗壓性)、最大使 用溫度、及化學抗性而言,符合此領域之主要需求。然而 ’保護性聚醯胺被覆對其纖維係由氟化聚合物組成之P0F 之不良粘著性成爲問題。在將光纜(p〇F加保護性被覆)置 於暴露於大溫度變化之環境(例如,機動車量之乘客車廂 )時,保護性被覆之弱粘著性特別不利,而且pop相對保 護性被覆移動’因爲其熱膨脹性質不同且聚醯胺對氟化聚 合物之粘著性不良。此結果之實例爲,P0F末端距發送器與 接收器(發光二極管/ P IN二極管)之距離有時太大使得發 生之強度失爲不可接受地局,而且在特定之情形造成資 料傳輸路徑中斷。此外,如果P0F脫離保護性被覆之移動 過度,則有損壞發送器或接收器之危險。 爲了降低此影響(稱爲P0F之「活塞化」),使用之 接頭、結合器或夾持具對保護性被覆施加大箝制或阻力, 因此增加保護性被覆與P0F間之磨擦。然而,所得之纖維 核與纖維殼間界面之變形造成增加之信號衰減。雖然在接 頭去除保護鞘可防止「活塞化」,其伴隨在組合時由於剝 除工具兩個刀面之不正確操作而損壞纖維殼之危險。 接頭對光纜施加之箝制或阻力亦可藉由對接頭外殻之 圓錐形孔中之P0F使用聯鎖固定法而降低。例如,一種提 議使用加熱板部份地熔化P0F末端,將所得熔化尖端壓入 200407574 朝接頭內部變窄之孔中,如此將P〇F堅固地固定在接頭外 殼內。然而,熔化且因此變形之區域中之P0F形狀有時由 圓柱形大爲分歧而造成全反射,因此在接頭外殻中發生增 加之強度損失。 DE 1 99 1 4 743 A1專利及相關之W〇0 0 / 6 0 3 8 2專利提 出此問題之解答。後者揭示具P0F (其具有纖維核且具有單 或多層纖維殻)及至少一個圍繞P0F之保護性被覆之光纜 ’其中纖維殼或至少其外層由氟化聚合物組成,及保護性 被覆由具低於220 °C之熔點之聚醯胺或共聚醯胺組成。此保 護性被覆不需要輔助即可粘著性於纖維殻,因爲聚醯胺之 殘基端基濃度不超過15微當量/克且胺基端基濃度在50至 300微當量/克之範圍。爲了使其可在最低熔化溫度擠製在 纖維殻上,這些用於W0 00 / 60382專利之聚醯胺具低黏度 。最大擠製溫度因此僅爲約185至200°C。W0 00 / 603 8 2專 利提及塡料(如碳黑)混合保護性被覆材料或保護性被覆 形成二或更多層之可能性,但是並無較特定本性之資訊。 然而,W0 00 / 60382專利中揭示之光纜具有許多缺點: •在所示之擠製溫度下並非始終可得適當之粘著性; •低黏度聚醯胺熔化物之擠製不產生足以得到張力下所需 粘著性之熔化壓力; •在提議之單層鞘不易得到市場要求之阻燃性,因爲通常 需要之阻燃性損及對纖維殼之粘著性,此外,光學衰減 受阻燃劑移動或阻燃劑顆粒對纖維殼之機械作用影響。 200407574 關於此先行技藝,此目的爲提供一種具有優良之保護 性被覆對纖維殼之粘著性,此外其具有均勻之保護性被覆 厚度之阻燃性POF。 (三)發明內容 此目的以實例之方式如第1圖所示,藉具有纖維核(i ) 且具有單或多層纖維殼(2 ),及包括至少以下額外層之光纜 而得: •內部外層(3 ),其堅固地粘著性於纖維殼及由包括聚醯胺 之模塑組成物組成,而且較佳爲實質上由聚醯胺組成, 其中 a)聚酿胺係選自 PA 11 、 PA 12 、 PA 1012 、 PA 1212 、以 這些聚醯胺爲主且含不超過30莫耳%共單體之共聚醯 胺、及其混合物; b )聚醯胺含至少5 0微當量/克之胺基端基,及 c )聚醯胺模塑組成物具有在2 20 °C依照ASTM D4440爲400 至6000 Pas,較佳爲500至3000 Pas,特佳爲600至 2000 Pas,而且特佳爲700至1200 Pas範圍之零剪切 力黏度; •外部外層(4 ),其以不超過3 0牛頓之剝除力粘著於內部 外層,而且由包括以下成分之聚醯胺模塑組成物組成: a) 2〇至95重量%之聚醯胺,其選自PA 1 1、PA 12、PA 1012 、PA 1212、以這些聚醯胺爲主且含不超過30莫耳%共 單體之共聚醯胺、以這些聚醯胺或共聚醯胺之一爲主 200407574 之聚醚醯胺、及其混合物, b) 5至45重量%之阻燃劑, c) 0至60重量%之衝擊改良劑, 其中百分比係fee a )、b )與◦)全部?十。 在第1圖僅以橫切面略示且未按比例所示之光纜特別 地作爲機動車輛之乘客車廂內可靠資料與信號傳輸用之傳 輸單位。纜線中存在之光學傳導結構爲已知爲逐步指引外 形光學導體者,例如,其在所示之實例中係由具1〇〇〇微米 區域直徑之PMMA纖維核1、及由氟化聚合物製造之單或多 層纖維殻2組成。纖維核1之光學衰減一般爲7 〇至1 〇 〇 d b / 公里(λ二5 7 0奈米)或125至i5〇 db/公里(λ = 6 5 0奈米) 〇 如同先行技藝,作爲殻材料或外部殻層之氟化聚合物 可爲氟化單體之均一聚合物或共聚物,或爲氟化單體與丙 細酸或與丙細酸之共聚物’或爲這些聚合物或共聚物之 混合物。可使用之特定氟化單體爲氟亞乙烯、四氟乙烷、 六氟丙院、甲基丙烯四氟丙酯、甲基丙烯五氟丙醋、甲基 丙烯三氟乙酯、甲基丙烯十七氟癸酯、或其混合物。 (四)實施方式 在一個可能之具體實施例中,殻材料包括聚氟亞乙烯 ,在適當之處混合PMMA或聚戊二醯亞胺(EPU 637 51 1 專利)或丙烯酸酯共聚物(ΕΡ-Α- 0 6 7 3 7 6 2專利)。 纖維核1及纖維殼2之外徑較佳爲對應IEC 6〇 7 9 3 _2 200407574 指定之標準(殼之外徑爲1 0 0 0 土 6 0微米;核直徑一般小10 至20微米;數値孔徑0 . 5± 0 · 1 5 ) °然而’亦可依照其他 標準値選擇纖維核1及纖維殻2之外徑(φ殼二7 5 0 土 4 5微米 或500土 30微米),或使其與開放巾暢場中配合使用指數 外形分等之POFs之尺寸一致(〇殼=75微米、1 25微米、250 微米、380微米、1500微米、2000微米、或3000微米)。 藉共擠製或串列擠製應用且圍繞P0F之外層3與4保 護本發明P0F ( 1 , 2 )不受外部影響。例如,內部外層3具有 2 00至300微米之厚度,而例如,外部外層4具有300至600 微米之厚度。在較佳具體實施例中,兩個外部層之厚度選 擇爲使得纜線之外徑爲2 . 2± 0 · 1毫米(Φ殼=1 000微米或750 微米)或1.5±0.1毫米(Φ殼= 500微米)。 形成內部外層3及作爲內部保護性被覆,而且對纖維 殼2之氟化聚合物具有良好粘著性之模塑組成物,包括胺 基端基濃度通常在50至500微當量/克範圍,較佳爲60至 300微當量/克範圍,而且特佳爲60至250微當量/克範圍 之聚醯胺。原則上,對羧基端基濃度並無限制,但是較佳 爲不超過30微當量/克,特佳爲不超過20微當量/克,而 且特別是不超過1 5微當量/克。過量之胺基端基係以已知 方法藉由在開始或縮聚(作用)時加入單或二胺而建立,此 單或二胺共聚合成爲鏈調節劑。適合之鏈調節劑較佳爲具 有一級胺基之任何單胺及二胺,例如,己胺、辛胺、乙基 己胺、十二碳胺、十三碳胺、二丁胺、硬脂胺、三丙酮二 200407574 胺、1,4 -二胺基丁院、1,6 -二胺基己烷、二胺基環己烷、 三甲基六亞甲二胺、1 , 8 -二胺基辛烷、1,〗〇 _二胺基癸烷、 1,1 2 -二胺基十二碳烷、間或對二甲苯二胺、環己基二亞甲 二胺、雙(對胺基環己基)甲烷、含2至44個碳原子(特 別是6至3 6個碳原子)之其他脂族、環脂族、或芳族單或 一胺、及這些胺之混合物。在PA 1 〇 1 2或PA 1 2 1 2之情形 ’使用超過化學計量之用量形成聚醯胺之二胺成分特別有 利。 用於本發明之聚醯胺爲先行技藝。p A 1 1係藉ω -胺基 十一碳酸之縮聚(作用)工業級製備,及PA 1 2係藉月桂內 醯胺之聚合製備,而ΡΑ 1012係藉1,1〇_癸二胺與1,12 -十 二碳酸之等莫耳混合物之縮聚(作用)製備,及PA i 2 1 2係 藉1,12 -十二碳二胺與1,12 -十二碳酸之等莫耳混合物之縮 聚(作用)製備。亦可使用以這些聚醯胺之一爲主且含不超 過30莫耳%共單體之共聚醯胺,此共單體係選自具有6至36 個碳原子之二羧酸、及具有6至36個碳原子之二胺、及具 有6至12個碳原子之胺基羧酸、及具有6至12個碳原子 之內醯胺。 用於內部外層3之模塑組成物除了聚醯胺亦可包括可 用之添加劑,如UV安定劑、熱安定劑、結晶加速劑、顏料 、與潤滑劑。在一個較佳具體實施例中,其塗成黑色(較 佳爲藉由加入碳黑)使得無外來光進入纖維核。 首先爲了在PMMA核之有限抗熱性所需之低熔化溫度得 200407574 到適當之粘著性,其次避免殼或核由於過度熔化壓力造成 橢圓形變形,依照ASTM D4440以機械光譜儀(單板)測量 ,模塑組成物在220°C之零剪切力黏度必須在400至6000 P a s範圍內,較佳爲在5 0 0至3 0 0 〇 P a s範圍內,特佳爲在 6 00至2000 Pas範圍內,而且特佳爲在700至1200 Pas範 圍內。 用於外部外層之聚醯胺及用於內部外層之聚醯胺可選 自相同之組合。然而,用於外部外層之聚醯胺亦可爲以這 些聚醯胺之一爲主之聚醚醯胺。聚醚醯胺原則上爲已知的 ,例如,得自DE-A 3 0 06 96 1專利。除了形成聚醯胺之單 體,聚醚醯胺之製備使用,例如,將對應聚醚二醇經還原 性胺化轉化,或偶合至丙烯腈繼而氫化(例如,EP - A - 0 4 3 4 244; EP-A- 0 29 6 8 5 2專利)而得到之聚醚二胺。聚醚二胺 通常具有230至4000之數量平均分子量,而且其在聚醚醯 胺中之含量較佳爲5至50重量%。 在適當之處,存在於用於外部外層之模塑組成物中之 阻燃劑可爲習知上用於聚醯胺模塑組成物之任何阻燃劑, 例如,聚鹵聯苯、聚鹵二苯醚、聚鹵酞酸或其衍生物、聚 鹵寡聚或聚碳酸酯、或鹵化聚苯乙烯,對應之溴化合物特 別有效;三聚氰胺三聚氰酸酯、三聚氰胺磷酸酯、三聚氰 胺焦磷酸酯、元素紅磷;有機磷化合物,如膦酸酯、次膦 酸酯、亞膦酸酯;氧化膦,如氧化三苯膦;膦、亞磷酸酯、 或磷酸酯,磷酸三苯酯。亦適合作爲阻燃劑之其他化合物 200407574 爲含磷-氮鍵者,例如,氯化磷腈、磷酸酯醯胺、磷酸醯 胺、膦酸醯胺、次膦酸醯胺、氧化参(吖啶基)膦、或氯 化肆(羥甲基)鱗。 如果使用鹵化阻燃劑,則可隨之使用基於模塑組成物 至多20%,較佳爲0 . 1至1 5重量%之量之協同劑。這些協同 劑可提及之實例爲鎘、鋅、鋁、銀、鐵、銅、銻、錫、鎂 、錳、釩、與硼之化合物。特別適合之化合物之實例爲所 提及金屬之氧化物,及碳酸鹽與氧碳酸鹽、氫氧化物、及 有機或無機酸之鹽,如乙酸鹽或磷酸鹽或磷酸氫鹽、與硫 酸鹽。 其他適合之阻燃劑爲鎂或鋁之氧化物水合物。 較佳爲使用無鹵素阻燃劑。 可使用之衝擊改良劑爲任何習知用於聚醯胺之型式。 例如,衝擊改良劑可選自以下種類之化合物: a) 具有20至96重量%乙烯含量,較佳爲25至85重量%乙 烯含量之乙烯-C3-C12-a-烯烴共聚物。所使用C3-C12-a-烯烴之實例爲丙烯、1 - 丁烯、1 -戊烯、丨_己烯、1 -辛烯 、卜癸烯、或1-十二碳烯。這些材料之典型實例爲乙烯 一丙烯橡膠及LLDPE。 b) 具有20至85重量%乙烯含量,,較佳爲25至75重量%乙 燔含量’及不超過約10重量%未共鞭二烯之乙嫌- C3-C12-a -嫌煙一未共轭二嫌三聚物,如雙環[2.2.1]庚二烯、1,4-己二烯、二環戊二烯、或特別是5 _亞乙基降冰片烯。適 200407574 合作爲c 3 ~ e 拉-納塔觸 藝。 c )含50至94 烯酸酯、及 他共單體之 ’ a )所述之 (例如,丙 酸單丁酯、 烯二酸酐或 噚唑啉或異 丙烯酸甘油 、或不飽和 参(2 -甲氧 氧基砂院、 藉自由 行技藝。 d )藉由將苯乙 苯乙燒一乙 e )聚伸烯基, 參見K . J .. Polymer 1sa Publishers 12、α -烯烴之化合物與a )所述相同。使用齊格 媒製備這些三聚物及a )所述共聚物爲先行技 重羹%乙烯、6至5 0重量%丙烯酸酯或甲基丙 〇至44重量% (較佳爲至20重量%)其 乙唏-丙烯酸酯共聚物,此共單體爲,例如 c 3 - C i 2 - α -烯烴、苯乙烯、不飽和單或二羧酸 烯酸、甲基丙烯酸、順丁烯二酸、順丁烯二 或伊康酸)、不飽和二羧酸酐(例如,順丁 伊康酸酐)、不飽和噚唑啉(例如,乙烯基 丙烯基噚唑啉)、不飽和環氧化物(例如, 酯、甲基丙烯酸甘油酯、或烯丙基噚氧烷) 矽烷(例如,乙烯基三甲氧基矽烷、乙烯基 基乙氧基)矽烷、3 -甲基丙烯氧基丙基三甲 或3 -甲基丙烯氧基丙基三乙氧基矽烷)。 基聚合製備這些乙烯-丙烯酸酯共聚物爲先 烯-丁二烯-苯乙烯嵌段共聚物氫化得到之 烯/ 丁烯-苯乙烯嵌段共聚物(SEBS)。 其可藉環烯屬烴之環開放或環膨脹聚合製備[ [vin、T. Saegusa 之”Ring-opening tion’’’ 第 1 卷,Elsevier Appl. Sci. ,倫敦,特別是第1 2 1- 1 8 3頁(1 9 8 4 )]。其中 -14- 200407574 較佳爲聚伸辛燃(參考資料A . D r S χ 1 e r之 Kautschuk+Gummi , Kunststoff 1981 ,第 185-190 頁) f )LDPE (高壓聚乙烯)。 g)具有超過 50重量%丁二烯含量之丙烯腈一 丁二烯-苯乙 烯(ABS)共聚物。 如同先行技藝,較佳地存在於衝擊改良劑中之官能基 可經共聚至主鏈中或藉熱或自由基途徑接枝至主鏈上之不 飽和單體引入。可鍵結至聚醯胺之特別適合之官能基爲羧 酸基、酐基、醯亞胺基、環氧基、噂唑啉基、或三烷氧基 矽烷基。廣泛種類之對應產物爲商業可得。 當然亦可使用各種衝擊改良劑之混合物。 此外,外部外層之模塑組成物亦可包括一般之添加劑 ’如UV安定劑、熱安定劑、結晶加速劑、塑性劑、潤滑劑 、無機塡料、或強化纖維。 在一個較佳具體實施例中,此模塑組成物包括用以使 組成物產生顏色之顏料,例如,綠色、黃色、藍色、紅色 、白色、或黑色。 內部外層必須堅固地粘著性於纖維殼,及此剝除力必 須爲至少50牛頓,而且較佳爲至少60牛頓。其係藉由使 用1 80至23 (TC之溫度(在模測量)將內部外層之模塑組成 物濟製於P〇F上而再現地得到。 相對地,外部外層與內部外層間必須有低粘著性,使 200407574 得其易於在,例如,接頭之區域,去除鞘。 剝除力必須不超過3 0牛頓,較佳爲不超過2 5牛頓, 而且特佳爲不超過20牛頓。例如,其可使用以下之手段得 到,其彼此無關: 1 .兩種模塑組成物之低相互相容性。例如,其一之結構係 以PA 1 1爲主,另一種則以PA 12爲主。用於外部外層 之模塑組成物之擠製溫度在模測量爲1 5 0至2 3 (TC之範 圍。 2 .兩種模塑組成物之良好相互相容性。在此情形,必須將 外部外層之模塑組成物在低到後者不發生初期熔化之溫 度擠製至內部外層上。有利之擠製溫度在模測量爲1 50 至2 0 0 °C之範圍,較佳爲1 6 0至1 9 0 °C之範圍。 3 ·外層之模塑組成物具有釋放劑。在此使用之釋放劑可爲 任何適合用於聚醯胺者,例如,硬脂·酸烷酯、硬脂酸鈣 、脂肪醯胺、酯、褐煤酸酯、蠘氧化物、或矽氧烷共聚 物。 使用以下之測試方法測試內部外層3對纖維殼2及外 部外層4對內部外層3之粘著性: •自約5 0 0毫米長度之纜線部份地剝除保護性被覆,使得 其餘保護性被覆之長度爲約3 0毫米; •使纜線之剝除部份通過板中之孔,孔之直徑各比纖維殻 或內部外層之外徑稍大; •將纜線之剝除端夾至張力測試機中(分離速率:1 〇毫米/ -16- 200407574 分鐘),及 •測量釋放保護性被覆所需之張力。 本發明在以下藉實例描述。 所有之實驗使用得自Nichimen( 1000B型)光續,其 由PMMA核及由PTFE層與PVDF層製造之殼組成。
聚醯胺之溶液黏度η , . e j係在2 0 °C於間甲苯酚之0 . 5強 度%重量比溶液測量。DSC熔點係在PerkinElmei· DSC 7機 器使用第2加熱曲線以20 K/分鐘加熱速率測定。C00H端 基係在熱苄醇中以鹼量測定法測定,及NH2端基係在間甲 苯酚中使用過氯酸測定。 1 .將內部外層3擠製至纖維1 . 2上 使用= 85、90微當量/克胺基端基與10微當量/
克酸端基之以ΡΑ 12爲主之模塑組成物(其已使用0· 3重 量%碳黑塗黑)完成之。依照ASTM D4440在220°C測量模塑 組成物之零剪切力黏度爲800 Pas。使用185 °C之溫度以30 公尺/分鐘之線性速度將此模塑組成物擠製至纖維上。 自纖錐剝除層3所需之力測定爲5 5牛頓/ 3 0毫米。 2 ·將外部外層4擠製至內部外層3卜 在1 8 5 °C之溫度以3 0公尺/分鐘之線性速度將下述模塑 組成物擠製至內部外層3上。 在各情形,自層3剝除層4所需之力測定爲小於3 0牛 頓/ 3 0毫米。 實例1 :由以下製造之模塑組成物 200407574 a) 100重量份如先行技藝由35.83公斤月桂內醯胺、6.45 公斤十二碳酸、與57 · 82公斤]EFFAMINE® D 2000 (聚醚 二胺;平均分子量2000 )製備之聚醚醯胺,其具有以下 之性質:
熔點(DSC) : 1 5 3〇C 相對溶液黏度η u i : 1.78 PA 12嵌段長度相當於1 5 09之平均分子量(由月桂 內醯胺/十二碳酸比例計算); b) 20重量份之MELAPUR,5,一種三聚氰胺三聚氰酸酯; c ) 0 . 5重量份之iraGNOX®1 〇 1 〇,一種安定劑。 測試結果室於表1。 1例_1":—由以下製造之模塑組成物 a)l〇〇重量份由80莫耳%月桂內醯胺與20莫耳%己內醯胺 製備之共聚醯胺;= 1 . 9; b ) 22 . 4重量份之MELAPUIT25 (三聚氰胺三聚氰酸酯), c) 〇.5重量份之IRAGNOX®1〇98(安定劑), d) 〇.2重量份之CEASIT®PC (硬脂酸鈣)。 參見表1。 見例3:由以下製造之模塑組成物 a) 58 重量份之 PA 12; rirel:=1.9; b) 40重量份之EXXELOR®VA1801(順丁烯二酸酐接枝EpM 橡膠); c) 15重量份之ANTIBLAZE®1045 (含磷阻燃劑) 200407574 d) 0 · 04重量份之CEASlfPC (硬脂酸鈣)。 參見表1。 實例…4: 一由以下製造之模塑組成物 a) 85 重量份之 PA 12; = l .6; b) 15重量份之MELAPUIT25 (三聚氰胺三聚氰酸酯), c) 15重量份之磷酸二苯基甲苯酚酯; d) 0.04重量份之CEASIT®PC (硬脂酸鈣)。 參見表1。 比較例1 在185°C及30公尺/分鐘將僅單層塗黑PA 12( T|rel = l . 66 ;零剪切力黏度400 Pas ; 40微當量/克之胺基端基)擠製 至纖維上。在產物上測定之粘著性爲25牛頓/ 30分鐘。 比較例2_ 步驟如比較例1,唯一之差異爲PA 1 2模塑組成物包括 20重量%之MELAPUR<§)25。發現纖維1,2變窄,因此具有不 良之光學傳輸品質。 寿 1 :—結果 實例 焰火測試[S] 酸儲存b) [d] 1 29 13 2 28 20 3 20 25 4 30 19 200407574 旦丄焰火測試係依照DamlerChrysler AG之線性光學導體用 測試步驟,第1 . 1版,第2 . 5 . 1項進行。顯示火燄熄滅 前經過之時間。 b )酸儲存係依照以上之測試步驟。顯示浸入纜線變脆前經 過之時間。 (五)圖式簡單說明 第1圖 本發明聚合物之光學導體剖面略圖 主要部分之代表符號 1 纖維核 2 纖維殼 3 內部外層 4 外部外層
Claims (1)
- 200407574 拾、申請專利範圍: 1 . 一種具聚合物光學導體之光纜,此導體具有纖維核且 具有單或多層纖維殼(2 ),其中纜線包括至少以下之額外 層: •內部外層(3 ),其堅固地粘著性於纖維殼及由包括聚醒 胺之模塑組成物組成,其中 a)聚醯胺係選自 PA 11、PA 12、PA 1012、PA 1212、 以這些聚醯胺爲主且含不超過30莫耳%共單體之 共聚醯胺、及其混合物; ® b )聚醯胺含至少5 0微當量/克之胺基端基,及 c)聚醯胺模塑組成物具有在220 °C依照ASTM D44 40 爲400至6000 Pas範圍之零剪切力黏度; •外部外層(4 ),其以不超過3 0牛頓之剝除力粘著性於 ’ 內部外層,而且由包括以下成分之聚醯胺模塑組成物 組成: a) 20至95重量%之聚醯胺,其選自PA 11、PA 12、ΡΑ φ 1012、PA 1212、以這些聚醯胺爲主且含不超過30 莫耳%共單體之共聚醯胺、以這些聚醯胺或共聚醯胺 之一爲主之聚醚醯胺、及其混合物’ b) 5至45重量%之阻燃劑, c) 0至60重量%之衝擊改良劑’ 其中百分比係按a )、b )與c )全部計° 2 .如申請專利範圍第1項之光纜’其中 200407574 內部外層(3)之聚醯胺模塑組成物具有5 00至3 000 Pas ^ 範圍之零剪切力黏度。 3 .如申請專利範圍第1項之光纜,其中 內部外層(3)之聚醯胺模塑組成物具有6 00至2000 Pas 範圍之零剪切力黏度。 4 .如申請專利範圍第1項之光纜,其中 內部外層(3)之聚醯胺模塑組成物具有7 00至1 200 Pas 範圍之零剪切力黏度。 5 .如以上任一項申請專利範圍之光纜,其中 ® 纖維核(1 )係由PMMA組成。 6 .如以上任一項申請專利範圍之光纜,其中 _ 纖維殼(2 )包括聚氟亞乙烯。 ^ 7 .如以上任一項申請專利範圍之光纜,其中 ~ 已將內部外層之模塑組成物塗黑。 -22-
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WO2001051977A2 (en) * | 1999-12-24 | 2001-07-19 | Mitsubishi Rayon Co., Ltd. | Optical fiber cable and optical fiber cable with plug |
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-
2002
- 2002-06-26 DE DE10228439A patent/DE10228439A1/de not_active Withdrawn
-
2003
- 2003-05-07 AT AT03010255T patent/ATE333102T1/de not_active IP Right Cessation
- 2003-05-07 DE DE50304190T patent/DE50304190D1/de not_active Expired - Lifetime
- 2003-05-07 EP EP03010255.2A patent/EP1376156B2/de not_active Expired - Lifetime
- 2003-06-18 MX MXPA03005503A patent/MXPA03005503A/es unknown
- 2003-06-24 BR BR0302122-0A patent/BR0302122A/pt not_active IP Right Cessation
- 2003-06-24 AU AU2003204916A patent/AU2003204916A1/en not_active Abandoned
- 2003-06-24 JP JP2003179908A patent/JP5140230B2/ja not_active Expired - Lifetime
- 2003-06-25 TW TW092117253A patent/TW200407574A/zh unknown
- 2003-06-25 CN CNB03148767XA patent/CN1324339C/zh not_active Expired - Lifetime
- 2003-06-25 KR KR1020030041372A patent/KR20040002672A/ko not_active Application Discontinuation
- 2003-06-26 US US10/603,710 patent/US6766091B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP1376156A3 (de) | 2004-05-12 |
MXPA03005503A (es) | 2004-09-06 |
CN1324339C (zh) | 2007-07-04 |
AU2003204916A1 (en) | 2004-01-22 |
JP5140230B2 (ja) | 2013-02-06 |
EP1376156B2 (de) | 2016-03-23 |
DE10228439A1 (de) | 2004-01-22 |
US6766091B2 (en) | 2004-07-20 |
KR20040002672A (ko) | 2004-01-07 |
EP1376156A2 (de) | 2004-01-02 |
JP2004029823A (ja) | 2004-01-29 |
ATE333102T1 (de) | 2006-08-15 |
DE50304190D1 (de) | 2006-08-24 |
EP1376156B1 (de) | 2006-07-12 |
US20040001682A1 (en) | 2004-01-01 |
CN1469150A (zh) | 2004-01-21 |
BR0302122A (pt) | 2004-08-17 |
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