201120274 六、發明說明： 【發明所屬之技術領域】 本發明關於藉由塗覆-凝聚製造多層傳導性纖維的兩 種選擇性方法，該纖維包含：（a)由天然或合成纖維形 成之核心，及（b)含有乙烯醇均或共聚物及奈米管（特 別是碳奈米管）之殻。本發明同樣關於該所得之纖維，以 及其用途。最後，本發明關於包括此類多層複合纖維之複 Q 合材料，其係藉由編織或利用聚合物基質而結合在一起。 【先前技術】 碳奈米管（或CNTs )眾所周知且具有管狀之特定結 晶構造，彼等爲封閉且中空，並由原子均勻排列成成五角 ' 形、六角形及/或七角形所組成，同時係由碳製得。 CNTs通常係由一或多層同軸滾壓的石墨片所組成。因此 ’有單壁奈米管（SWNTs )及多壁奈米管（MWNTs )的 區別。 CNTs已商品化並可藉由已知方法製備。有數種方法 可用於合成碳奈米管’特別是放電、雷射剝蝕、及化學蒸 氣沉積（或CVD)，該方法可使碳奈米管大規模製造， 所以可和碳奈米管之大量使用相呼應而以成本價取得。此 方法精確地係由在相對高溫下將碳來源注射在觸媒上所組 成’而觸媒本身係由金屬諸如鐵 '鈷、鎳或鉬承載於無機 固體（諸如氧化鋁、二氧化矽或氧化鎂）上所組成。碳來 源可包括甲烷、甲烷 '乙烷、乙烯、乙炔、乙醇、生物乙 -5- 201120274 醇、甲醇或甚至是一氧化碳與氫之混合物（HiPCO方法） 〇 C N T s具有許多高性能特性，也就是電、熱、化學及 機械性能。在其應用中特別可提及的有複合材料，彼等特 別可用於汽車、海運及航空工業、電機驅動器、電纜、電 阻導線、化學探測器、能量之儲存及轉換、電子發射器顯 示器、電子組件及功能性織物。在汽車、航空及電子領域 中，諸如CNTs之傳導性塡充劑能使熱的熱量和電耗散， 並在摩擦發生時放電。 一般而言，C N T s在合成時係爲由糾纏之纖維絲所組 成的碎裂粉末形式，因此較難使用。特別地，爲了開發 CNTs之機械及/或電特性，在宏觀面，CNTs需有大數量 且需被導向優勢的方向。 減輕此問題的解決方案之一在於製造複合纖維。爲了 達成此事，可將碳奈米管摻入基質（諸如有機聚合物）中 。然後根據已知技術進行擠壓，例如揭示於EP -1 1 8 1 3 3 1 號者’該技術係藉由伸長及/剪切操作使CNTs沿著纖維 的軸而定向，藉此獲得廣受歡迎的機械及/或電特性。然 而，此技術需要高純度CNTs並排除凝集體，凝集體會因 CNTs的糾纏結構而易於形成。這些凝集體實際上對紡絲 過程有害，並經常導致所得之複合纖維斷裂。 再者，根據前述技術所獲得之複合纖維的傳導性並非 總是令人滿意。事實上，當C N T s均勻且無規地分散時， 其電特性可進一步增進，然而，在另一方面紡絲過程卻導 -6- 201120274 致CNTs顯著的定向。 製造傳導性複合纖維的另一方法在於經由溶劑將 CNTs沉積於預形成之纖維上。然而，當這些複合纖維用 於製造織物時，本身會被堆疊數層以形成用於航空或汽車 領域的結構部件或煞車碟，舉例之，這些部件在空氣中或 在地面上的摩擦會引起纖維的磨損。此將導致CNTs在大 氣中損耗，部件的環境碰撞也會產生問題，及可能減低部 0 件之機械特性。 製造以CNT爲基礎之複合纖維的又一方法在於使分 散於聚合物流（諸如聚（乙烯醇））之CNTs分散液凝聚 (FR 2 805 1 79號）。然而，此凝聚方法無法獲得現今常 用之高擠壓速度。因爲從層狀流動轉變成高速湍流，及同 樣地因爲新凝聚之纖維在黏稠介質中的脆性，所以確實很 難穩定CNT分散液及凝聚溶液的同向流動。 最後，Xue 在 Composite Structures No. 78，271-277 〇 ( 2007 )之專刊文獻係揭示一種塗覆天然或合成纖維之方 法，其包括第一步驟爲以含有聚（乙烯醇）或PVA及 CNTs的組成物浸漬纖維，接著之步驟爲乾燥該等纖維， 然後藉由使該經浸漬之預纖維通入一於無機鹽水溶液中含 有甲醛的浴槽而將PVA乙醯化。此方法沒有包括任何凝 聚步驟，而結果是CNTs與纖維的附著不良，因此形成不 均勻且不堅固的沉積物’而使該已塗覆之纖維較難處理及 乾燥。 爲了克服此一缺點，Xue所揭示之方法包括乙醯化步 201120274 驟。此導致P v A的交聯，而變得不可溶且更加剛硬’同 時也更脆及更少可變形’因此在所得之纖維必須用於織物 製造的情況中造成不利的條件。再者’經由封閉PVA鏈 ，交聯步驟會限制該等所得之纖維的導電率。由於不希望 受到任何一種理論限制，本申請者認爲在該等奈米管之間 的已交聯PVA產生機械性安定之絕緣層，而阻止奈米管 互相拉引得更靠近以傳送電流。而且，在高溫下此已交聯 之PVA比其他傳導性纖維顯現較沒有改進之傳導率。 最終，Xue所揭示之方法的經濟效益將受到中間的纖 維乾燥步驟及甲醛的必需使用而有負面影響，甲醛之使用 需要與此化合物之毒性相稱的設備。 舉例之，在FR 1 261 926號文獻中已提出，在使以 PVA爲基礎之纖維進行乙醯化處理之前，應藉由將此纖維 通入一含有硼酸鹽之浴槽而使該纖維凝聚。然而，此文獻 旨在增進該等纖維對熱水之耐性，並沒有揭示傳導性纖維 ，而且也不管含有CNTs之纖維。 基於所有上述之原因，對具有良好機械特性（特別是 在應力下之高牽引模數）和高韌性，及可能地良好耐熱性 及/或耐化學性，且同時具有足夠之傳導率以使複合纖維 縱使在低奈米管特性下還能驅散靜電荷的複合纖維仍存有 需求。同樣地對隨意地在高速度下製造此纖維之穩定且具 經濟性方法也存有需求，該方法將因奈米管聚集體之存在 而些微地受影響。 -8 - 201120274 【發明內容】 本申請人發現，此需求可藉由使用特定之塗覆-凝聚 方法而解決。 因此，根據第一個方向，本發明之目標係一種製造多 層傳導性纖維的方法，該纖維包含： - 由天然或合成纖維形成之核心’ - 含有乙烯醇均或共聚物及選自週期表Ilia、IVa 0 及Va欄元素中之至少一種化學元素之奈米管的殼’ 其特徵爲該方法包含下列步驟： 1 - 在與該奈米管共價或非共價鍵結之安定劑存在下 ，將奈米管分散於溶劑及該乙烯醇均或共聚物中’以形成 塗覆組成物， 2- 藉由該塗覆組成物塗覆該天然或合成纖維’以形 成複合預纖維（pre-fibre)， 3- 將該複合預纖維通入包括有至少一種凝聚劑之無 Q 甲醛的凝聚溶液中，以形成多層預纖維’ 4- 萃取、隨意地清洗、及乾燥該多層預纖維，以獲 得多層纖維。 根據第二個方向，本發明關於一種製造多層傳導性纖 維的方法，該纖維包含： - 由天然或合成纖維形成之核心’ - 含有乙烯醇均或共聚物及選自週期表〗IIa、IVa 及Va欄元素中之至少一種化學元素之奈米管的殼’ 其特徵爲該方法包含下列步驟： -9 - 201120274 1 - 隨意地在分散劑存在下將奈米管分 以形成塗覆組成物， 2- 藉由該塗覆組成物塗覆該天然或合 成複合預纖維， 3- 將該複合預纖維通入包括有至少一 包括該乙烯醇均或共聚物）之無甲醛的凝聚 成多層預纖維， 4- 萃取、隨意地清洗、及乾燥該多層 得多層纖維。 可清晰地明瞭，在不會負面影響該傳導 成的範圍內，據本發明之方法可能包括上文 步、中間及/或隨後之步驟。 作爲緒言性陳述，在整個說明中可特另 之間”之描述應解釋爲包括該規定之限制。 再者，在本發明定義內，“纖維”一詞 100與300微米（μπι)之間的股，以在1 間較佳，且以2與50微米之間更佳。就纖 纖維係意圖確保機械部件之強度及增強機械 同於欲運送流體之管子或管線。 所以，根據本發明之方法關於一種藉由 成纖維並接著進行凝聚以製造多層傳導性纖 天然或合成纖維之實例可選自下列： - 合成之聚合物纖維，其特別含有： (i )聚（乙烯醇）或聚（乙酸乙烯酯） 散於溶劑中， 成纖維，以形 種凝聚劑（其 溶液中，以形 預纖維，以獲 性複合纖維形 提及之其他初 :的是，“在… 系表示直徑在 胃100微米之 維用途來說， 部件，因此不 塗覆天然或合 維的方法。 -10- 201120274 (ii )聚醯胺，諸如聚醯胺6 ( PA-6 ) PA-11)、聚醯胺12(PA-12)、聚醯胺6 聚醯胺 4.6 (PA-4.6)、聚醯胺 6·1〇(ΡΑ-< 6-12( PA-6.12 )，芳族聚醯胺，特別是薄 (尤其是聚（對-伸苯基對苯二甲醯胺）或 族聚醯胺（aramide )，及嵌段共聚物，特 醚，201120274 VI. Description of the Invention: [Technical Field] The present invention relates to two selective methods for producing multilayer conductive fibers by coating-coacervation, the fibers comprising: (a) a core formed of natural or synthetic fibers, And (b) a shell comprising a vinyl alcohol homo- or copolymer and a nanotube (especially a carbon nanotube). The invention is also directed to the resulting fibers, and their uses. Finally, the invention relates to complex Q-containing materials comprising such multilayer composite fibers which are bonded together by weaving or using a polymeric matrix. [Prior Art] Carbon nanotubes (or CNTs) are well known and have a specific crystal structure of a tube, which is closed and hollow, and is composed of atoms uniformly arranged in a pentagonal shape, a hexagonal shape, and/or a heptagon shape. Made from carbon. CNTs are typically composed of one or more layers of coaxially rolled graphite sheets. Therefore, there are differences between single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). CNTs have been commercialized and can be prepared by known methods. There are several methods for synthesizing carbon nanotubes, especially discharge, laser ablation, and chemical vapor deposition (or CVD). This method allows large-scale fabrication of carbon nanotubes, so it can be used in large quantities with carbon nanotubes. In response, it is obtained at a cost price. This method is precisely composed of injecting a carbon source onto a catalyst at a relatively high temperature, and the catalyst itself is carried by a metal such as iron 'cobalt, nickel or molybdenum on an inorganic solid such as alumina, ceria or oxidized. Made up of magnesium). Carbon sources may include methane, methane 'ethane, ethylene, acetylene, ethanol, bio-B-5-201120274 alcohol, methanol or even a mixture of carbon monoxide and hydrogen (HiPCO method) 〇CNTs have many high-performance properties, namely electricity , thermal, chemical and mechanical properties. Particularly useful in their applications are composite materials, which are particularly useful in the automotive, marine and aerospace industries, motor drives, cables, resistive wires, chemical detectors, energy storage and conversion, electron emitter displays, electronic components. And functional fabrics. In the automotive, aerospace and electronics sectors, conductive chelators such as CNTs dissipate heat and electricity and discharge when friction occurs. In general, C N T s is synthesized in the form of a fragmented powder composed of entangled filaments, and thus is difficult to use. In particular, in order to develop the mechanical and/or electrical properties of CNTs, in the macroscopic aspect, CNTs need to have a large number of directions that need to be directed. One of the solutions to alleviate this problem is to make composite fibers. In order to achieve this, the carbon nanotubes can be incorporated into a matrix such as an organic polymer. Extrusion is then carried out according to known techniques, for example as disclosed in EP-1 1 8 1 3 3 1 'This technique is used to orient the CNTs along the axis of the fiber by elongation and/or shearing operations, thereby gaining widespread acceptance Welcome mechanical and / or electrical characteristics. However, this technique requires high purity CNTs and excludes aggregates, which are easily formed by the entangled structure of CNTs. These aggregates are actually harmful to the spinning process and often cause the resulting composite fibers to break. Moreover, the conductivity of the composite fiber obtained according to the foregoing technique is not always satisfactory. In fact, when C N T s is uniformly and randomly dispersed, its electrical properties can be further improved, however, on the other hand, the spinning process leads to a significant orientation of CNTs. Another method of making conductive composite fibers consists in depositing CNTs onto the preformed fibers via a solvent. However, when these composite fibers are used in the manufacture of fabrics, they are themselves stacked several layers to form structural components or brake discs for use in the aerospace or automotive field. For example, the friction of these components in the air or on the ground causes fibers. Wear and tear. This will result in loss of CNTs in the atmosphere, environmental impacts of the components, and the mechanical properties of the parts. Yet another method of making CNT-based composite fibers is to agglomerate CNTs dispersions dispersed in a polymer stream, such as poly(vinyl alcohol) (FR 2 805 1 79). However, this coacervation method cannot achieve the high extrusion speeds that are commonly used today. It is difficult to stabilize the co-flow of the CNT dispersion and the coagulation solution because of the transition from lamellar flow to high-speed turbulence and, similarly, to the brittleness of the newly coagulated fibers in the viscous medium. Finally, Xue, in the special issue of Composite Structures No. 78, 271-277 (2007), discloses a method of coating natural or synthetic fibers comprising the first step of containing poly(vinyl alcohol) or PVA and CNTs. The composition impregnates the fibers, followed by drying the fibers, and then oxidizing the PVA by passing the impregnated pre-fiber into a bath containing formaldehyde in an aqueous solution of the inorganic salt. This method does not include any coagulation steps, and as a result, the CNTs are poorly attached to the fibers, thus forming a non-uniform and unstable deposit' which makes the coated fibers more difficult to handle and dry. In order to overcome this shortcoming, the method disclosed by Xue includes the steps of 201120274. This results in cross-linking of P v A, which becomes insoluble and more rigid 'at the same time more brittle and less deformable' and thus causes unfavorable conditions in the case where the resulting fibers have to be used in the manufacture of fabrics. Furthermore, by blocking the PVA chain, the crosslinking step limits the conductivity of the resulting fibers. Since it is not desired to be bound by any theory, the Applicant believes that the crosslinked PVA between the nanotubes produces a mechanically stable insulating layer that prevents the nanotubes from pulling closer together to carry current. Moreover, this crosslinked PVA exhibits a less improved conductivity than other conductive fibers at elevated temperatures. Ultimately, the economic benefits of the method disclosed by Xue will be adversely affected by the intermediate fiber drying step and the necessary use of formaldehyde, which requires equipment commensurate with the toxicity of this compound. For example, it has been proposed in the document FR 1 261 926 that the fibers are agglomerated by passing the fibers into a bath containing borate prior to subjecting the PVA-based fibers to acetonitrile treatment. However, this document aims to improve the resistance of such fibers to hot water, and does not reveal conductive fibers, and does not matter the fibers containing CNTs. For all of the above reasons, it has good mechanical properties (especially high traction modulus under stress) and high toughness, and possibly good heat resistance and/or chemical resistance, and at the same time has sufficient conductivity to make the composite There is still a need for fibers that can dissipate static charge in the presence of low nanotube characteristics. There is also a need for a stable and economical process for the manufacture of such fibers at high speeds arbitrarily, which will be slightly affected by the presence of nanotube aggregates. -8 - 201120274 SUMMARY OF THE INVENTION The Applicant has found that this need can be solved by using a specific coating-coacervation method. Thus, according to a first direction, the object of the invention is a method for producing a multilayer conductive fiber comprising: - a core formed from natural or synthetic fibers - containing a vinyl alcohol homo- or copolymer and selected from the periodic table Ilia a shell of a nanotube of at least one of the elements of the IVa 0 and Va columns, characterized in that the method comprises the following steps: 1 - in the presence of a stabilizer covalently or non-covalently bonded to the nanotube Dispersing a nanotube in a solvent and the vinyl alcohol homo- or copolymer to form a coating composition, 2- coating the natural or synthetic fiber by the coating composition to form a composite pre-fiber (pre- Fibre), 3- The composite pre-fiber is passed into a Q-formaldehyde-free coacervate solution comprising at least one coagulant to form a multilayer pre-fiber '4-extract, optionally washed, and dried to obtain the multilayer pre-fiber Multilayer fiber. According to a second aspect, the invention relates to a method of producing a multilayer conductive fiber comprising: - a core formed from natural or synthetic fibers - containing a vinyl alcohol homo- or copolymer and selected from the Periodic Tables IIa, IVa and a shell of a nanotube of at least one of the chemical elements of the Va column element, characterized in that the method comprises the following steps: -9 - 201120274 1 - Optionally, the nanotubes are separated in the presence of a dispersant to form a coating composition, 2- coating the natural or synthetic composite pre-fiber by the coating composition, 3- introducing the composite pre-fiber into a formaldehyde-free condensed multi-layer pre-fiber comprising at least one of the vinyl alcohol homo- or copolymer , 4- Extracting, optionally washing, and drying the multi-layered multi-layer fibers. It will be apparent that the method according to the invention may include the above, intermediate and/or subsequent steps, without thereby adversely affecting the conductance. As an introductory statement, the description of the entire description may be construed as including the limitation of the specification. Furthermore, within the definition of the invention, the term "fiber" is between 100 and 300 microns (μπι). The strands are preferably between 1 and preferably between 2 and 50 microns. The fiber is intended to ensure the strength of the mechanical parts and to enhance the mechanical or tubular or pipeline to which the fluid is to be transported. Therefore, the method according to the invention Examples of a multi-layered conductive natural or synthetic fiber by fiber formation followed by agglomeration may be selected from the following: - a synthetic polymer fiber, which specifically contains: (i) poly(vinyl alcohol) or poly(acetic acid) Vinyl ester) dispersed in a solvent, into a fiber, in the form of a coagulant (in solution, in the form of a pre-fiber, in the form of a replenishing composite fiber mentioned in the other beginning: "in... represents the diameter in the stomach 100 In the case of micron dimensions, the parts are therefore not coated with natural or dimensional methods. -10- 201120274 (ii) Polyamines such as polyamine 6 (PA-6) PA-11), polyamido 12 (PA-12), Polyamine 6 Polyamide 4.6 (PA-4. 6), polyamine 6·1〇 (ΡΑ-< 6-12 (PA-6.12), aromatic polyamine, especially thin (especially poly(p-phenylphenylphthalamide)) Or aramide, and block copolymers, special ethers,
〇 ( iii )聚烯烴，諸如高密度聚乙烯、I /或丙燦共聚物，隨意地使之官能化， (iv)聚酯諸如聚羥基烷酸酯， (v )聚芳基醚酮（PAEK ) ’諸如聚 (peek)及聚（芳基醚酮酮）（ρεκκ)， (Vi )氟聚合物，特別係選自下列： (a)包含至少5〇莫耳％之至少一 者： ❹ CFXi=CX2X3 (I) 其中X丨、X2及X3各別表示氫或鹵素β 或氯），諸如聚（偏二氟乙烯）（PVDF) 佳），聚（三氟乙烯）（PVF3 ) ’聚（ PTpE)，偏二氟乙烯與六氟丙烯（HFP ) VF3)、四氟乙烯（TFE)、氯三氟乙烯（ 物’氟乙烯/丙烯（FEP )共聚物，乙烯與 FEP)或四氟乙烯（TFE)、或氯三氟乙稀 聚物； 、聚醯胺1 1 ( •6 ( pA-6.6 )、 5 · 1 0 )、聚醯胺 $鄰苯二甲醯胺 Kevlar®)和芳 別是聚酿胺/聚 资丙烯和乙烯及 (芳基醚醚酮） 種式（I )單體 《子（特別是氟 (以α形式較 四氟乙烯）（ 、三氟乙烯（ CTFE )之共聚 氟乙烯/丙烯（ (CTFE)之共 -11 - 201120274 (b )包含至少50莫耳％之至少一種式（II ) 者： R-0-CH-CH2 (II) 其中R表示全鹵化烷基（特別是全氟化），諸如 丙基乙烯醚（PPVE)、全氟乙基乙烯醚（P EVE)、 烯與全氟（甲基乙烯醚）（PMVE )之共聚物， (vii)熱塑性聚胺基甲酸酯（TPU)， (vi ii )聚對苯二甲酸乙二酯或聚對苯二甲酸丁 (ix )聚丙烯腈（P AN )， (X)丙烯酸系聚合物， (xi )聚（氯乙烯）； - 碳纖維； - 玻璃纖維，特別是E、R或S 2型； - 硼纖維； - 矽石纖維 - 天然纖維，諸如亞麻、大麻、壇麻、棉、羊 絲；及 - 上述物質之混合物，諸如玻璃、碳及芳族聚 (aramide)纖維之混合物或彼等之慘合物。 上述之合成纖維可根據熟諳此藝者已知之任何纖 成方法而製造，特別是藉由熔融紡絲（通常是藉由擠 或溶液、或其他藉由凝聚而製造，如文獻FR 2 8〇5 號及FR 2 92 1 975號所揭示般。 單體 全氟 及乙 二酯 毛或 醯胺 維形 壓） -12- 179 201120274 這些纖維將進行塗覆-凝聚過程，彼等 纖維紡絲系統即隨意地連續執行塗覆-凝聚 含有選自週期表Ilia、IVa及Va欄元素中 學元素之奈米管的乙烯醇均或共聚物層來塗 這些奈米管因著其特性及品質，必須能 電之傳導。彼等可包含碳、硼、磷及/或氮 化物、碳化物、磷化物），舉例之，彼等係 0 化硼、碳化硼、磷化硼、氮化磷或氮化硼碳 於本發明而言，以碳奈米管（本文以下稱爲 〇 根據本發明所用之奈米管可爲單壁、雙 。特定言之，雙壁奈米管可如Flahaut等人^ (2003 )，1442所揭示般製備。至於多壁奈 文獻WO 03/02456號般製備。 奈米管通常具有平均直徑在0.1至200: 圍內，以0.1至100奈米較佳，0.4至50奈 1至30奈米又更佳，及較有利地是具有0.1 〆m )之長度。彼等之長度/直徑比較佳地仿 常地係大於1 〇〇。具例之，彼等之比表面穆 3 00 m2/g之間，及視密度特定地在0.05與 ，而以在〇·1與0.2 g/m3之間更佳。舉例之 可包括5至15個薄片（或壁），而以7至] 。這些奈米管可經加工處理或未經處理。 原料型碳奈米管之實例已商品化，可特 一旦離開這些 過程，其係以 之至少一種化 覆該等纖維。 確保熱及/或 (硼化物、氮 由氮化碳、氮 所組成。對用 CNTs)較佳 壁或多壁形式 匕 Chem. Com. 米管，則可如 奈米（n m )範 米更佳，且以 至10微米（ S大於1 〇，最 【係在100與 0.5 g/m3 之間 ，多壁奈米管 [0個薄片更佳 定地以商品名 -13- 201120274〇 ( iii ) polyolefin, such as high density polyethylene, I / or propylene copolymer, optionally functionalized, (iv) polyester such as polyhydroxyalkanoate, (v) polyaryl ether ketone (PAEK 'A peek and a poly(aryl ether ketone ketone) (ρεκκ), (Vi) fluoropolymer, in particular selected from the group consisting of: (a) at least one of at least 5 〇 mol%: ❹ CFXi =CX2X3 (I) wherein X丨, X2 and X3 each represent hydrogen or halogen β or chlorine), such as poly(vinylidene fluoride) (PVDF), poly(trifluoroethylene) (PVF3) 'poly(PTpE) ), vinylidene fluoride and hexafluoropropylene (HFP) VF3), tetrafluoroethylene (TFE), chlorotrifluoroethylene ("fluoroethylene/propylene (FEP) copolymer, ethylene and FEP) or tetrafluoroethylene (TFE) ) or chlorotrifluoroethylene; polyamine 1 1 ( •6 ( pA-6.6 ), 5 · 1 0 ), polyamine 0 phthalic acid Kevlar®) and aromatic Brewing amine/polypropylene and ethylene and (aryl ether ether ketone) species (I) monomer "especially fluorine (in alpha form than tetrafluoroethylene) (, trifluoroethylene (CTFE) copolymerized vinyl fluoride /propylene (compared to (CTFE)-1 1 - 201120274 (b) comprising at least 50 mol% of at least one formula (II): R-0-CH-CH2 (II) wherein R represents a perhalogenated alkyl group (especially perfluorinated) such as propyl ethylene Ether (PPVE), perfluoroethyl vinyl ether (P EVE), copolymer of alkene and perfluoro(methyl vinyl ether) (PMVE), (vii) thermoplastic polyurethane (TPU), (vi ii Polyethylene terephthalate or polybutylene terephthalate (ix) polyacrylonitrile (P AN ), (X) acrylic polymer, (xi) poly(vinyl chloride); - carbon fiber; - glass fiber , especially E, R or S 2 type; - boron fiber; - vermiculite fiber - natural fiber such as flax, hemp, algae, cotton, sheep silk; and - a mixture of the above substances, such as glass, carbon and aromatic a mixture of aramide fibers or a mixture thereof. The synthetic fibers described above may be made according to any of the methods known to those skilled in the art, in particular by melt spinning (usually by extrusion or solution, Or otherwise produced by coacervation, as disclosed in documents FR 2 8〇5 and FR 2 92 1 975. Monomeric perfluoro and ethylene diester hair or醯 维 维 ) -12- 179 201120274 These fibers will undergo a coating-coacervation process, and their fiber spinning systems will optionally perform continuous coating-agglomeration containing elements selected from the columns Iia, IVa and Va of the periodic table. The vinyl alcohol or copolymer layer of the nanotubes is coated with these nanotubes because of their characteristics and quality, and must be electrically conductive. They may include carbon, boron, phosphorus and/or nitrides, carbides, phosphides, for example, they are boron, boron carbide, boron phosphide, phosphorus nitride or boron nitride carbon in the present invention. In terms of carbon nanotubes (hereinafter referred to as 〇, the nanotubes used in accordance with the present invention may be single-walled, double-shaped. In particular, double-walled nanotubes may be as in Flahaut et al. (2003), 1442 It is prepared as disclosed. It is prepared as described in WO 2004/02456. The nanotubes usually have an average diameter of 0.1 to 200: within the range of 0.1 to 100 nm, preferably 0.4 to 50 to 1 to 30 nm. More preferably, and more advantageously, having a length of 0.1 〆m). Their length/diameter is generally better than 1 〇〇. For example, their specific surface area is between 300 m2/g, and the apparent density is specifically 0.05 and the ratio is better between 〇·1 and 0.2 g/m3. Examples may include 5 to 15 sheets (or walls) and 7 to]. These nanotubes can be processed or untreated. Examples of feedstock type carbon nanotubes have been commercialized, and once they have left these processes, at least one of them is coated. Ensure that heat and / or (boron, nitrogen consists of carbon nitride, nitrogen. For CNTs) better wall or multi-wall form 匕Chem. Com. rice tube, then better than nano (nm) van Mi And even 10 microns (S is greater than 1 〇, most [between 100 and 0.5 g/m3, multi-walled nanotubes [0 slices are better settled under the trade name -13-201120274
Graphistrength® C100 而自 ARKEMA 公司取得。 這些奈米管在進行根據本發明之方法前，可經純化及 /或加工處理（即氧化）及/或硏磨。選擇性或額外地， 彼等可經官能化，特定地係爲了增進與天然或合成纖維之 附著。 當這些奈米管是冷或熱時都可特定地進行硏磨，並可 根據所利用之已知技術在裝置諸如球磨機、鎚磨機、輪碾 機、切碎機、噴氣磨粉機或可減小奈米管之糾纏網狀物尺 寸的任何其他硏磨系統中進行。此硏磨步驟較佳地係根據 噴氣硏磨技術進行，且特定地係在噴空氣磨粉機或球磨機 中進行。 原料型或已硏磨之奈米管的純化可藉由以硫酸溶液清 洗而進行，以除掉由該等奈米管製備方法所產生之可能的 殘留礦物質或金屬雜質。奈米管對硫酸之重量比可特定在 1 : 2與1 : 3之間。此外，純化操作可在90至120°C範圍 內的溫度下進行達5至1 0小時的時間。此一操作有利地 可接續用水沖洗及乾燥該純化奈米管的步驟。可選擇性地 ，奈米管可藉由高溫熱處理來純化’典型地係大於1 〇〇〇 〇C。 奈米管之氧化作用較有利地係藉由與含有0 · 5至1 5 重量％ NaOCl之次氯酸鈉溶液接觸而進行，而以1至10 重量％ NaOCl較佳，亦即奈米管對亞氯酸鈉之重量比在1 :〇. 1至1 : 1範圍內。氧化較有利地係在低於6 0 °C之溫 度下（而以常溫較佳）進行數分鐘至24小時的時間。此 -14- 201120274 氧化操作有利地可接續過濾及/或離心、清洗及乾燥該已 氧化之奈米管的步驟。 爲了消除金屬觸媒殘留物，同樣可行的是使奈米管進 行至少l〇〇〇°C (亦即1 200°C )之熱處理。 隨意地經硏磨之原料型奈米管較佳地可用於本發明中 ，也就是不經氧化也不純化不官能化且沒有進行任何其他 化學及/或熱處理的奈米管。 Q 奈米管相對於殼之重量可占有0.1至70重量％，以1 至50重量％較佳，且以2至30重量％更佳》 在根據本發明之第一步驟中，這些奈米管係分散於溶 劑中，以形成塗覆組成物。 溶劑較佳地係選自水、二甲基亞楓（DMSO )、甘油 、乙二醇、二乙二醇、三乙二醇、二伸乙基三胺、乙二胺 、苯酚、二甲基甲醯胺（DMF)、二甲基乙醯胺、N -甲基 吡咯啶酮及彼等之混合物。溶劑較佳地係選自水、D M S 〇 〇 、及彼等之所有比例的混合物。 若是水性分散液，則該水性分散液之pH可藉由加入 一或多種酸類而較佳地維持在3與5之間，這些酸類係選 自無機酸諸如硫酸、硝酸及鹽酸，有機酸諸如乙酸、酒石 酸及草酸，及有機酸與有機酸鹽之混合物諸如檸檬酸與檸 檬酸鈉、乙酸與乙酸鈉、酒石酸與酒石酸鉀、酒石酸與檸 檬酸鈉。 將奈米管分散於溶劑中在常溫下進行，或舉例之’在 40與120°C之間的溫度下。 -15- 201120274 根據來自本發明的好處之一，將奈米管分散於溶劑中 可利用超音波或轉子-定子系統或球磨機而產生或增進。 特定言之，此類轉子-定子系統係由SILVERSON公司以商 品名Silverson® L4RT販售。另一形式之轉子-定子系統 係由IKA-WERKE公司以商品名Ultra-Turrax®販售。尙 有其他轉子-定子系統係由膠體磨粉機、抗絮凝渦輪及轉 子-定子形式高剪切混合器所組成，例如IKA-WERKE公 司或ADMIX公司販售之裝置。 在根據本發明之塗覆-凝聚方法中，所用之天然或合 成纖維並不僅是以奈米管塗覆，還同樣地以乙烯醇均或共 聚物（其以聚（乙烯醇）較佳）塗覆。爲了更加簡易化， 本文以下將聚（乙烯醇）命名爲“PVA”，應明瞭的是此一 命名同樣包括乙烯醇共聚物。 PVA可包含在塗覆組成物或凝聚溶液中。 在本發明之第一具體實施例中，PVA係包含在塗覆組 成物中。爲了防止奈米管在PVA存在下太早凝聚，該塗 覆組成物可包含至少一種安定劑。 在本發明定義內，“安定劑”乃表示一種能使奈米管均 勻分散於溶液中之化合物，該安定劑可保護奈米管在乙烯 醇均或共聚物存在下不會凝聚，但卻無法阻止乙烯醇均或 共聚物在凝聚溶液中凝聚。 根據本發明之該或該等安定劑係共價或非共價地與奈 米管鍵結。 在安定劑係非共價地與奈米管鍵結之情況中，該安定 -16- 201120274 劑可選自實質爲非離子性之表面活性劑。 在本發明定義內，舉例來說“實質爲非離子性之表面 活性劑”應明瞭係表示在 w〇rk 2008 McCutche〇n’s “Emulsifiers and. Detergents，”所引用之非離子性兩親媒 性化合物（其較佳地具有HLB (親水親油性平衡）爲1 3 至1 6 )，以及含有親水性嵌段及親油性嵌段且具有低離 子性（亦即〇至1 〇重量％離子性單體及99至1 00%非離 子性單體）的嵌段共聚物。 ^ 舉例之，在本發明範圍內，非共價地與奈米管鍵結之 該或該等安定劑可選自下列： (i )多元醇酯，特別是： - 脂肪酸與山梨聚糖酯，隨意地經聚乙氧基化， • - 脂肪酸與甘油酯， - 脂肪酸與蔗糖酯， - 脂肪酸與聚乙二醇酯， (Π )經聚醚改質之聚矽氧烷， 〇 (iii )脂肪醇與聚乙二醇酯， (iv) 烷基聚糖苷， (v) 聚乙烯-聚乙二醇嵌段共聚物， (vi) 特別揭示於申請案WO 2005/ 1 0848 5號之嵌段 共聚物，也就是包含至少一種帶有離子性或可電離官能之 嵌段1者，其係衍生自占有至少1 0重量％之嵌段1 (諸 如（甲基）丙烯酸或馬來酐）之Ml單體與至少一種M2 單體（諸如（甲基）丙烯酸酯或苯乙烯衍生物），及隨意 -17- 201120274 地含至少一種與聚（乙烯醇）相容之嵌段2(假若嵌段1 不能相容時）的聚合反應。 在安定劑係共價地與奈米管鍵結之第二情況中’該安 定劑較佳地含有親水性基團，且較有利地爲接枝在奈米管 上之聚乙二醇基團。 將反應性單元諸如聚乙二醇基團接枝在奈米管表面可 根據熟諳此藝者已知之任何方法來進行。舉例之，熟諳此 藝者將可參考B. Zhao等人之專刊文獻（Synthesis and Characterization of Water Soluble Single-Walled Carbon Nanotube Graft Copolymers，J. Am, Chem. Soc. ( 2 0 0 5 ) Vol. 127 No. 22)。根據此專刊文獻，係將奈米管分散於 二甲基甲醯胺（DMF )並與草醯氯接觸。在第二階段中， 係將所得之分散液與聚乙二醇（PEG )接觸。純化該依此 接枝之奈米管。 在本發明之第二具體實施例中，如先前所述，PVA可 包含在凝聚溶液中。 在此具體實施例中，塗覆組成物包括在溶劑（諸如先 前所述者）中之奈米管，且較佳地同樣包括至少一種分散 劑，該分散劑係意圖促進奈米管分散於溶劑中並可特定地 選自下列：乙烯基吡咯啶酮均及共聚物；含有至少一種陰 離子親水性單體及至少一種疏水性單體的共聚物，諸如文 獻FR-2 766 1 06號所揭示之聚合物；表面活性劑；及彼 等之混合物。 在根據本發明方法之第二步驟中，該含有奈米管、溶 -18- 201120274 劑及隨意地PVA、安定劑及/或分散劑之塗覆組成物可藉 由熟諳此藝者已知之任何工具而施加到所用之天然或合成 纖維上，特別是藉由將該等纖維通入由該塗覆組成物所組 成之浸渍浴中，或藉由將該塗覆組成物噴射到該等纖維上 〇 纖維也可使用單絲纖維形式、或人造短纖維形式或由 二-或-三個方向網絡之纖維所組成的梭織或非梭織結構， 0 或其他的針織結構形式。 根據本發明方法之第三步驟在於將該於塗覆步驟完成 時所得的複合預纖維，通入包括有至少一種凝聚劑之無甲 醛的凝聚溶液中，以形成多層預纖維。 在本發明定義內，“凝聚溶液”應明瞭係表示一能使含 奈米管之殼凝固的靜態槽或流動形式之溶液。 此類溶液是熟諳此藝者所知悉。根據本發明之具體實 施例之一，凝聚溶液包括選自水、醇、多元醇、酮及彼等 Q 之混合物的溶劑，更佳地係選自水、甲醇、乙醇、丁醇、 丙醇、異丙醇、二醇、丙酮、甲基乙基酮、甲基異丁基酮 、苯、甲苯及彼等之混合物的溶劑，甚而更佳地係選自水 、甲醇、乙醇、二醇、丙酮及彼等之混合物的溶劑。 若凝聚溶液之溶劑實質地爲水，則凝聚溶液較有利的 溫度在1 0與80°c之間。若凝聚溶液之溶劑實質地爲有機 溶劑，諸如甲醇，則凝聚溶液較有利的溫度在-3 0與1 0°C 之間。 在上述之第一具體實施例中，PVA係用於該塗覆組成 -19 - 201120274 物的情況下，凝聚劑可選自能使P V A凝聚的鹽類，諸如 鹼性鹽及/或脫水鹽，特別是硫酸銨、硫酸鉀、硫酸鈉、 碳酸鈉、及彼等之混合物。 在第二具體實施例中，凝聚劑爲PVA本身。 將根據本發明方法之第二步驟完成時所得的複合預纖 維導入凝聚溶液，可依類似於熟諳此藝者已知之技術而進 行，以經由凝聚作用形成纖維。一般來說，用於凝聚單絲 纖維之最常用的技術有濕紡法（舉例之，可參閱專利 US 3,8 50,90 1 號、US 3,852,402 號及 US 4,6 12，157 號）及 乾噴射式濕紡法（舉例之，可參閱專利US 4,603,083號 、US 4,698,194 號、US 4,971,861 號、US 5,208,104 號及 US 7,026,049號）。所以熟諳此藝者可進行這些技術以演 練本發明。這些技術可藉由使用具有通向欲塗覆之合成纖 維且共中心排列於附近的出口、通向塗覆組成物之出口的 噴絲頭而執行。此噴絲頭可浸沒或不浸沒在凝聚溶液中， 端視噴絲頭操作係在濕或乾燥環境中進行而定。所以，應 明瞭此凝聚步驟可在根據本發明之方法的第二步驟之後以 連續方式進行。 不考慮已執行之本發明具體實施例時，塗覆組成物及 /或凝聚溶液可進一步含有一或多種化合物，這些化合物 乃意於增進所製造之多層纖維的機械特性（特別是抽拉能 力）及/或耐水性或耐溫度性，及/或促進該等纖維之凝 聚或紡絲。此類化合物之實例包括硼酸及其鹽類（特別是 鹼性者）、強鹼諸如氫氧化鈉或氫氧化鉀及彼等之混合物 -20- 201120274 根據本發明方法之第三步驟完成時所得的多層預纖維 接下來將連續地或非連續地被萃取’然後隨意地清洗一或 多次。清洗槽較佳地含有水。清洗步驟可使預纖維的一部 份外圍聚合物被清除，藉此使具有傳導性層之奈米管組成 物更豐富地塗覆在纖維上（可高至70重量％ )。再者， 清洗槽也可包括能使此傳導性層之組成物被改質之試劑， 0 或能在化學上互相作用之試劑。特別地，可將化學或物理 交聯劑（特別是硼酸鹽）加入於該槽中以增強傳導性層。 此清洗步驟也可使那些試劑（特別是表面活性劑）被清除 ，這些試劑選擇性地對纖維之機械或電特性有害。 乾燥步驟同樣地含括於根據本發明之方法中。此步驟 可在萃取操作後立刻進行，或連續地隨著清洗操作。特定 而言，若欲獲得富合聚合物之纖維，則較合宜的是在萃取 後立刻乾燥預纖維。乾燥操作較佳地在烤箱中進行，該烤 〇 箱係因烤箱內部導管之內的氣體循環而使預纖維乾燥。乾 燥操作也可經由紅外線輻射進行。 根據本發明之方法同樣地包括纏繞步驟，及可能地在 乾燥步驟與纏繞步驟之間進行的熱拉步驟。 纏繞之前，多層傳導性纖維可進一步進行欲使該纖維 表面官能化的上膠步驟，以增加該纖維與聚合物基質（因 該纖維必須與聚合物基質一起浸漬）相容性。 一旦完成上述之方法，即可獲得多層傳導性纖維。此 類纖維同樣也是本發明之目標。 -21 - 201120274 這些多層傳導性纖維可用於製造火箭或飛機的鼻部、 機翼或座艙；近海軟管裝甲；汽車本體、汽車之引擎底盤 部件或托架片；汽車座椅護套；建築或橋操及道路之領域 的結構組件；包裝用品及抗靜電織物，特別是抗靜電窗簾 、抗靜電衣服（例如，安全用途或用於無塵室）或用於保 護筒倉或包裝及/或運輸粉末或顆粒物質的材料；像倶元 件’特別是用於無塵室傢倶；濾器；電磁防護裝置，特別 是用於保護電子組件者；加熱織物；傳導電纜；感應器， 特別是變形或機械應力感應器：電極；氫儲存裝置；或生 物醫學器件諸如縫合線、輔具或導管。 這些複合部件之製造可根據各種方法來進行，通常牽 涉到將根據本發明之傳導性複合纖維浸漬在含有至少一種 熱塑性、彈性或熱固性物質的聚合物組成物中之步驟。此 浸漬步驟本身可根據各種技術而進行，特定地係以所用之 聚合物組成物的物質形式（粉狀或或多或少地是液體）爲 基礎。傳導性複合纖維之浸漬較佳地係根據流化床浸漬法 來進行，其中聚合物組成物爲粉末狀態。對聚合物浸漬基 質而言，更佳的是包括那些用來製造如本發明之多層傳導 性纖維的熱塑性物質中之至少一者。 依此可獲得半完成品，彼等接著係用來製造所欲之複 合部件。各種具有相同或不同組成之預浸漬的纖維織物可 堆疊起來以形成平板或層壓物質’或選擇性地進行熱成形 過程。選擇性地，可將預浸漬纖維組合起來以形成長條’ 藉由將這些長條纏繞在具有欲製造之部件形狀的心軸四周 -22- 201120274 ’而用於能獲得幾乎沒有形狀限制之中空部件的纖維絲纏 繞製程。 在另一選擇性方法中’可行的是自該浸漬聚合物組成 物中製備薄膜，特別地係利用擠壓或壓延方法，舉例之， 該薄膜具有約100微米厚度’然後將該薄膜放置在兩個如 本發明之傳導性複合纖維的墊子之間，接著熱壓整個組合 件以確保該等纖維之浸漬及複合部件之製造。 在這些方法中，根據本發明之傳導性複合纖維可單獨 地或與其他纖維一起進行梭織或針織，或單獨使用或與其 他纖維組合，以製造氈製品或非梭織材料。包含這些其他 纖維之材料的實例可選自先前引述之含有天然或合成纖維 的材料。 所以’本發明之另一目標係一種包括上文所述之多層 複合纖維的複合材料，該等纖維係藉由編織或利用聚合物 基質而結合在一起。 【實施方式】 藉由下列非限制性且純屬解說性之實施例，並與隨附 之圖結合將可更加瞭解本發明，其中 - 圖1顯示根據本發明之塗覆有CNT之纖維的光 學顯微照片。 - 圖2顯示根據先前技術之塗覆有CNT之纖維的 光學顯微照片。 -23- 201120274 實施例 實施例1:製造塗覆有CNT之纖維（方法1 ) 將碳奈米管（ARKEMA 公司之 Graphistrength® C100 )分散於使用1 %非離子性表面活性劑（聚氧乙烯硬脂醯 基醚（20 OE) (Brij® 78))之1重量％比率的水中。 將此混合物曝露於超音波2小時。所得之分散液很安定且 均勻。接著與含有2重量％PVA之聚（乙烯醇）（PVA) 水溶液混合。將所得之塗覆組成物沉積在直徑1 〇〇微米之 聚醯胺纖維上。然後將該已塗覆之纖維通入由Na2S04水 溶液（3 00 g/Ι )所組成之凝聚浴中。 如圖1所示，該纖維在整個長度上很均勻且具傳導性 。測得之表面傳導率的數値爲30 ohms/sp.。 實施例2:製造塗覆有CNT之纖維（方法2 ) 將碳奈米管（ARKEMA 公司之 Graphistrength® C100 )分散於使用1 %陰離子性表面活性劑（十二烷基硫酸鈉 )之1重量％比率的水中。將此混合物曝露於超音波2小 時。所得之分散液很安定且均勻。將所得之塗覆組成物沉 積在直徑100微米之聚醯胺纖維上。然後將該已塗覆之纖 維通入由聚（乙烯醇）水溶液所組成之凝聚浴中。 該纖維在整個長度上很均勻且具傳導性。測得之表面 傳導率爲2 ohms/sp.。 實施例3 :製造塗覆有CNT之纖維（比較實施例） -24- 201120274 將碳奈米管（ARKEMA 公司之 Graphistrength® C100 )分散於1重量％比率之聚（乙烯醇）（PVA )水溶液中 。將此混合物曝露於超音波2小時。縱使在此處理後，該 分散液並不安定且肉眼可看到奈米管之附聚物。將此塗覆 組成物施加到直徑1 〇〇微米之聚醯胺纖維上。所得之沉積 物非常不均勻。 如圖2所示，該纖維的某些部份有CNT附聚物存在 0 時，將具傳導性，然而缺乏CNTs的其他部份則呈絕緣。 此系統並非全部具傳導性，因爲絕緣部份阻止電流沿著纖 維流通。 【圖式簡單說明】 圖1顯示在實施例1中所製造之纖維。 圖2顯示在實施例3 (比較實施例）中所製造之纖維 -25-Graphistrength® C100 was obtained from ARKEMA. These nanotubes may be subjected to purification and/or processing (i.e., oxidation) and/or honing prior to carrying out the process according to the invention. Alternatively or additionally, they may be functionalized, in particular to enhance adhesion to natural or synthetic fibers. These nanotubes can be specifically honed when they are cold or hot, and can be used in equipment such as ball mills, hammer mills, wheel mills, choppers, jet mills or according to known techniques utilized. Performed in any other honing system that reduces the size of the entangled mesh of the nanotubes. This honing step is preferably carried out according to a jet honing technique, and in particular in an air jet mill or a ball mill. Purification of the raw material or honed nanotubes can be carried out by washing with a sulfuric acid solution to remove possible residual minerals or metallic impurities produced by the preparation of the nanotubes. The weight ratio of the nanotube to sulfuric acid can be specified between 1:2 and 1:3. Further, the purification operation can be carried out at a temperature in the range of 90 to 120 ° C for a period of 5 to 10 hours. This operation advantageously provides the step of rinsing and drying the purified nanotubes with water. Alternatively, the nanotubes can be purified by high temperature heat treatment 'typically greater than 1 〇〇〇 〇C. The oxidation of the nanotubes is advantageously carried out by contacting with a solution of sodium hypochlorite containing 0.5 to 15% by weight of NaOCl, preferably 1 to 10% by weight of NaOCl, i.e., nanotubes to chlorous acid. The weight ratio of sodium is in the range of 1: 〇. 1 to 1: 1. Oxidation is advantageously carried out at a temperature below 60 ° C (and preferably at normal temperature) for a period of from several minutes to 24 hours. This -14-201120274 oxidation operation advantageously provides the step of subsequently filtering and/or centrifuging, washing and drying the oxidized nanotubes. In order to eliminate metal catalyst residues, it is also possible to subject the nanotubes to a heat treatment of at least 10 ° C (i.e., 1 200 ° C). Optionally honed raw material nanotubes are preferably used in the present invention, i.e., nanotubes which are not oxidized or purified and which are not functionalized and which are not subjected to any other chemical and/or heat treatment. The Q nanotubes may comprise from 0.1 to 70% by weight, preferably from 1 to 50% by weight, more preferably from 2 to 30% by weight, relative to the weight of the shell. In the first step according to the invention, the nanotubes It is dispersed in a solvent to form a coating composition. The solvent is preferably selected from the group consisting of water, dimethyl sulfoxide (DMSO), glycerin, ethylene glycol, diethylene glycol, triethylene glycol, diethylene ethylamine, ethylenediamine, phenol, dimethyl Methionamine (DMF), dimethylacetamide, N-methylpyrrolidone, and mixtures thereof. The solvent is preferably selected from the group consisting of water, D M S 〇 、 , and mixtures thereof in all ratios. In the case of an aqueous dispersion, the pH of the aqueous dispersion can be preferably maintained between 3 and 5 by the addition of one or more acids selected from the group consisting of inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid, and organic acids such as acetic acid. , tartaric acid and oxalic acid, and mixtures of organic acids and organic acid salts such as citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate, tartaric acid and sodium citrate. The nanotubes are dispersed in a solvent at a normal temperature, or exemplified by a temperature between 40 and 120 °C. -15- 201120274 According to one of the benefits from the present invention, dispersing the nanotubes in a solvent can be produced or enhanced by means of an ultrasonic or rotor-stator system or a ball mill. In particular, such rotor-stator systems are sold by SILVERSON under the trade name Silverson® L4RT. Another form of rotor-stator system is sold under the trade name Ultra-Turrax® by the company IKA-WERKE.尙 Other rotor-stator systems consist of a colloid mill, a deflocculating turbine, and a rotor-stator high shear mixer, such as those sold by IKA-WERKE or ADMIX. In the coating-coacervation method according to the present invention, the natural or synthetic fibers used are not only coated with a nanotube, but also coated with a vinyl alcohol homo- or copolymer (which is preferably poly(vinyl alcohol)). cover. For the sake of simplicity, poly(vinyl alcohol) is hereinafter referred to as "PVA", and it should be understood that this designation also includes a vinyl alcohol copolymer. The PVA can be included in the coating composition or coacervate solution. In a first embodiment of the invention, the PVA is included in the coating composition. In order to prevent the nanotubes from coagulating too early in the presence of PVA, the coating composition may comprise at least one stabilizer. Within the definition of the present invention, "stabilizer" means a compound which enables a uniform dispersion of a nanotube in a solution which protects the nanotube from agglomeration in the presence of a vinyl alcohol or copolymer but does not The vinyl alcohol homopolymer or copolymer is prevented from agglomerating in the coagulation solution. The stabilizer or the stabilizer according to the present invention is bonded to the nanotube covalently or non-covalently. In the case where the stabilizer is non-covalently bonded to the nanotube, the stabilizer -16 - 201120274 agent may be selected from substantially nonionic surfactants. Within the definition of the present invention, for example, "substantially nonionic surfactants" shall be taken to mean nonionic amphiphilic compounds cited in W〇rk 2008 McCutche〇n's "Emulsifiers and. Detergents," (It preferably has an HLB (hydrophilic-lipophilic balance) of from 1 3 to 16), and contains a hydrophilic block and a lipophilic block and has low ionicity (that is, 〇 to 1% by weight of ionic monomer) And a block copolymer of 99 to 100% nonionic monomer). For example, within the scope of the invention, the stabilizer or non-covalently bonded to the nanotube may be selected from the group consisting of: (i) a polyol ester, in particular: - a fatty acid and a sorbitan ester, Optionally polyethoxylated, • - fatty acids and glycerides, - fatty acids and sucrose esters, - fatty acids and polyethylene glycol esters, (Π) polyether modified polyoxyalkylene, 〇 (iii) fat Alcohols with polyethylene glycol esters, (iv) alkyl polyglycosides, (v) polyethylene-polyethylene glycol block copolymers, (vi) block copolymers specifically disclosed in application WO 2005/1 0848 5 , that is, a block comprising at least one block having an ionic or ionizable function, which is derived from a M1 sheet containing at least 10% by weight of block 1 such as (meth)acrylic acid or maleic anhydride And at least one M2 monomer (such as (meth) acrylate or styrene derivative), and optionally -17-201120274 contains at least one block 2 compatible with poly(vinyl alcohol) (if block 1 cannot Polymerization when compatible). In the second case where the stabilizer is covalently bonded to the nanotube, 'the stabilizer preferably contains a hydrophilic group, and more advantageously a polyethylene glycol group grafted onto the nanotube. . Grafting a reactive unit such as a polyethylene glycol group onto the surface of the nanotube can be carried out according to any method known to those skilled in the art. For example, those skilled in the art will be referred to the B. Zhao et al. (Synthesis and Characterization of Water Soluble Single-Walled Carbon Nanotube Graft Copolymers, J. Am, Chem. Soc. (200) Vol. No. 22). According to this special publication, a nanotube is dispersed in dimethylformamide (DMF) and contacted with grass chloroform. In the second stage, the resulting dispersion is contacted with polyethylene glycol (PEG). The thus-grafted nanotubes were purified. In a second embodiment of the invention, the PVA may be included in the coagulation solution as previously described. In this particular embodiment, the coating composition comprises a nanotube in a solvent, such as those previously described, and preferably also includes at least one dispersant intended to facilitate dispersion of the nanotubes in the solvent. And may be specifically selected from the group consisting of vinylpyrrolidone homo- and copolymers; copolymers comprising at least one anionic hydrophilic monomer and at least one hydrophobic monomer, such as disclosed in document FR-2 766 1 06 a polymer; a surfactant; and a mixture thereof. In a second step of the method according to the invention, the coating composition comprising a nanotube, a solution of -18-201120274 and optionally a PVA, a stabilizer and/or a dispersant may be known by any of the artisan skilled in the art. Applying the tool to the natural or synthetic fibers used, in particular by passing the fibers into an impregnation bath consisting of the coating composition, or by spraying the coating composition onto the fibers The rayon fibers may also be in the form of monofilament fibers, or staple fibers, or woven or non-woven structures composed of fibers of a two- or three-direction network, 0 or other knit constructions. The third step of the process according to the invention consists in passing the composite pre-fiber obtained at the completion of the coating step into a coagulum-free coagulation solution comprising at least one coagulant to form a multilayer pre-fibres. Within the definition of the invention, "agglomerating solution" shall be taken to mean a solution in a static tank or in the form of a flow which will enable the solidification of the shell containing the nanotubes. Such solutions are known to those skilled in the art. According to one embodiment of the invention, the coacervation solution comprises a solvent selected from the group consisting of water, alcohols, polyols, ketones and mixtures of Q thereof, more preferably selected from the group consisting of water, methanol, ethanol, butanol, propanol, a solvent of a mixture of isopropanol, diol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene and the like, even more preferably selected from the group consisting of water, methanol, ethanol, glycol, acetone And solvents for their mixture. If the solvent of the coagulation solution is substantially water, the coagulation solution is advantageously at a temperature between 10 and 80 °C. If the solvent of the coacervate solution is substantially an organic solvent such as methanol, the coagulation solution is advantageously at a temperature between -3 0 and 10 °C. In the first specific embodiment described above, in the case where the PVA is used for the coating composition -19 - 201120274, the coagulant may be selected from salts capable of agglomerating PVA, such as basic salts and/or dehydrated salts, In particular, ammonium sulfate, potassium sulfate, sodium sulfate, sodium carbonate, and mixtures thereof. In a second embodiment, the coagulant is the PVA itself. The introduction of the composite pre-fiber obtained upon completion of the second step of the process of the present invention into a coacervate solution can be carried out in accordance with techniques known to those skilled in the art to form fibers via coacervation. In general, the most common technique for agglomerating monofilament fibers is the wet spinning process (for example, see US Pat. Nos. 3,8 50,90 1 , US 3,852,402 and US 4,6 12,157) and In the case of a spray-type wet-spinning method (for example, see US Pat. No. 4,603,083, US Pat. No. 4,698,194, US Pat. No. 4,971,861, US Pat. No. 5,208,104, and US Pat. No. 7,026,049). Therefore, those skilled in the art can carry out these techniques to practice the present invention. These techniques can be carried out by using a spinneret having an outlet leading to the synthetic fibers to be coated and co-centered in the vicinity, leading to the outlet of the coating composition. The spinneret can be submerged or not submerged in the coagulation solution, depending on whether the spinneret operating system is in a wet or dry environment. Therefore, it should be understood that this coacervation step can be carried out in a continuous manner after the second step of the process according to the invention. Regardless of the specific embodiment of the invention that has been practiced, the coating composition and/or coacervate solution may further comprise one or more compounds which are intended to enhance the mechanical properties (especially the drawability) of the multilayered fibers produced. And/or water resistance or temperature resistance, and/or promote coagulation or spinning of the fibers. Examples of such compounds include boric acid and its salts (especially basic), strong bases such as sodium hydroxide or potassium hydroxide, and mixtures thereof - 20 to 201120274, obtained upon completion of the third step of the process according to the invention The multilayer pre-fibers will then be continuously or discontinuously extracted 'and then optionally washed one or more times. The cleaning tank preferably contains water. The cleaning step allows a portion of the peripheral polymer of the pre-fiber to be removed, thereby allowing the nanotube composition having the conductive layer to be more abundantly coated on the fiber (up to 70% by weight). Further, the cleaning tank may also include a reagent capable of modifying the composition of the conductive layer, 0 or a chemically reactive reagent. In particular, a chemical or physical crosslinking agent, particularly a borate, can be added to the tank to enhance the conductive layer. This cleaning step also allows those agents (especially surfactants) to be removed which are selectively detrimental to the mechanical or electrical properties of the fibers. The drying step is likewise included in the process according to the invention. This step can be carried out immediately after the extraction operation or continuously with the cleaning operation. In particular, if a fiber of a polymer-rich polymer is desired, it is more desirable to dry the pre-fiber immediately after the extraction. The drying operation is preferably carried out in an oven which dries the pre-fibers due to gas circulation within the conduits inside the oven. Drying operations can also be carried out via infrared radiation. The method according to the invention likewise comprises a winding step, and possibly a hot drawing step between the drying step and the winding step. Prior to entanglement, the multilayer conductive fibers may be further subjected to a sizing step to functionalize the surface of the fibers to increase the compatibility of the fibers with the polymer matrix (since the fibers must be impregnated with the polymer matrix). Once the above method is completed, a multilayer conductive fiber can be obtained. Such fibers are also an object of the present invention. -21 - 201120274 These multi-layer conductive fibers can be used to make the nose, wing or cockpit of a rocket or aircraft; offshore hose armor; automotive body, engine chassis components or brackets; automotive seat sheaths; Structural components in the field of bridge operations and roads; packaging and antistatic fabrics, especially antistatic curtains, antistatic clothing (for example, for safe use or for clean rooms) or for protection of silos or packaging and/or transportation a material of powder or particulate matter; such as a crucible element 'especially for use in clean room furniture; filters; electromagnetic protection devices, especially for protecting electronic components; heating fabrics; conducting cables; inductors, especially deformation or machinery Stress sensor: electrode; hydrogen storage device; or biomedical device such as suture, accessory or catheter. The manufacture of these composite parts can be carried out according to various methods, generally involving the step of immersing the conductive composite fibers according to the present invention in a polymer composition containing at least one thermoplastic, elastomeric or thermosetting substance. This impregnation step itself can be carried out according to various techniques, in particular based on the form of the polymer composition used (powdered or more or less liquid). The impregnation of the conductive composite fibers is preferably carried out according to a fluidized bed impregnation method in which the polymer composition is in a powder state. More preferably, for the polymer impregnated matrix, at least one of those used to make the multilayered conductive fibers of the present invention. Semi-finished products are thus obtained, which are then used to make the desired composite parts. A variety of pre-impregnated fiber fabrics having the same or different compositions can be stacked to form a flat sheet or laminate material' or selectively subjected to a thermoforming process. Alternatively, the pre-impregnated fibers can be combined to form strips 'by wrapping the strips around the mandrel having the shape of the part to be fabricated -22-201120274' for hollowing out with virtually no shape restrictions The filament winding process of the part. In another alternative method, it is feasible to prepare a film from the impregnated polymer composition, in particular by extrusion or calendering, for example, the film has a thickness of about 100 microns ' and then place the film in two Between the mats of the conductive composite fibers of the present invention, the entire assembly is then hot pressed to ensure impregnation of the fibers and manufacture of the composite parts. In these methods, the conductive composite fibers according to the present invention may be woven or knitted, either alone or in combination with other fibers, or used alone or in combination with other fibers to produce a felt or non-woven material. Examples of materials comprising these other fibers may be selected from previously cited materials containing natural or synthetic fibers. Therefore, another object of the present invention is a composite material comprising the above-described multilayer composite fibers which are bonded together by weaving or using a polymer matrix. The invention will be further understood by the following non-limiting and purely illustrative examples, and in conjunction with the accompanying drawings, in which Figure 1 shows the optics of CNT-coated fibers in accordance with the present invention. micrograph. - Figure 2 shows an optical micrograph of a CNT coated fiber according to the prior art. -23- 201120274 EXAMPLES Example 1: Production of CNT-coated fibers (Method 1) Carbon nanotubes (ARKEMA's Graphistrength® C100) were dispersed in a 1% nonionic surfactant (polyoxyethylene hard) Lipidyl ether (20 OE) (Brij® 78)) in a 1% by weight ratio of water. The mixture was exposed to ultrasound for 2 hours. The resulting dispersion is very stable and uniform. It was then mixed with a poly(vinyl alcohol) (PVA) aqueous solution containing 2% by weight of PVA. The resulting coating composition was deposited on a polyamide fiber having a diameter of 1 μm. The coated fibers were then passed through a coagulation bath consisting of a solution of Na2SO4 (300 g/Ι). As shown in Figure 1, the fibers are very uniform and conductive throughout their length. The measured surface conductivity is 30 ohms/sp. Example 2: Production of CNT-coated fibers (Method 2) Carbon nanotubes (Augry's Graphistrength® C100) were dispersed in 1% by weight using 1% anionic surfactant (sodium dodecyl sulfate) The ratio of water. This mixture was exposed to ultrasound for 2 hours. The resulting dispersion is very stable and uniform. The resulting coating composition was deposited on polyamine fibers having a diameter of 100 μm. The coated fibers are then passed into a coagulation bath consisting of an aqueous solution of poly(vinyl alcohol). The fiber is very uniform and conductive throughout its length. The measured surface conductivity was 2 ohms/sp. Example 3: Production of CNT-coated fibers (Comparative Example) -24- 201120274 Dispersion of carbon nanotubes (Graphstrength® C100 of ARKEMA) in a 1% by weight ratio of poly(vinyl alcohol) (PVA) aqueous solution . The mixture was exposed to ultrasound for 2 hours. Even after this treatment, the dispersion was not stable and the agglomerates of the nanotubes were visible to the naked eye. This coating composition was applied to a polyamide fiber having a diameter of 1 μm. The resulting deposits are very uneven. As shown in Figure 2, some parts of the fiber will have conductivity when there is a CNT agglomerate of 0, while other parts lacking CNTs will be insulated. This system is not all conductive because the insulating portion prevents current from flowing along the fiber. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the fibers produced in Example 1. Figure 2 shows the fiber produced in Example 3 (Comparative Example) -25-