WO2017133225A1 - 同轴导电弹性复合长丝及其制备方法 - Google Patents

同轴导电弹性复合长丝及其制备方法 Download PDF

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Publication number
WO2017133225A1
WO2017133225A1 PCT/CN2016/096993 CN2016096993W WO2017133225A1 WO 2017133225 A1 WO2017133225 A1 WO 2017133225A1 CN 2016096993 W CN2016096993 W CN 2016096993W WO 2017133225 A1 WO2017133225 A1 WO 2017133225A1
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Prior art keywords
conductive
layer
composite filament
elastic
coaxial
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PCT/CN2016/096993
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English (en)
French (fr)
Inventor
包磊
肖学良
周思佳
包松
包宇洲
汪亮
汪理
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深圳市善行医疗科技有限公司
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Publication of WO2017133225A1 publication Critical patent/WO2017133225A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products

Definitions

  • the present invention relates to the field of composite fiber technology, and in particular, to a coaxial conductive elastic composite filament having excellent electrical conductivity, good elasticity, large deformation, and shielding function, and a preparation method thereof.
  • the relevant human physiological signals such as electrocardiogram (ECG), blood oxygen saturation (Sp0 2 ) and blood pressure data parameters are sent to the hospital monitoring center through the wireless network, and the monitoring center receives the signal and then responds to the emergency rescue.
  • ECG electrocardiogram
  • Sp0 2 blood oxygen saturation
  • blood pressure data parameters are sent to the hospital monitoring center through the wireless network, and the monitoring center receives the signal and then responds to the emergency rescue.
  • the wire has good electrical conductivity, but it is easy to give a prickle feeling when it is added to a textile for wearing.
  • DuPont Company of the United States successfully produced composite organic polymer conductive fibers with carbon black as the conductive core layer by using composite spinning technology for antistatic textiles and electromagnetic shielding applications.
  • the polymer conductive fiber avoids the discomfort caused by the modulus problem in the wearing textile, and can quickly and reversibly respond under external stimulation in the conductive channel, and has the potential of intelligent and multifunctional real-time monitoring, plus preparation Low cost, good weaving and washing resistance, and bright application prospects.
  • the composite spinning technique can be prepared by layering conductive particles and conventional polymers.
  • a conductive component carbon nanotube, carbon black, etc.
  • a masterbatch containing a conductive component is blended with a polymer matrix, and further spun to obtain a conductive fiber (CN1569939A, CN1438363A, CN101158058A,
  • CN1584140A and CN1563526A Generally speaking, it is necessary to add a higher content of conductive powder to the object. In the blending melt, the electrical properties of the conductive fibers are improved, which not only makes the spinning melt filterability worse, but also makes the spinning difficult, and the mechanical properties of the fibers are greatly reduced.
  • the conductive fiber prepared by wet spinning has a low electrical conductivity (CN1450210A), and the later coating on the fiber surface is simple or deposits a conductive layer. In actual use, the conductive effect is easily interfered by the outside, and the conductive layer is also easy. Fall off.
  • the fiber can be prepared into a large number of microporous structures, and then the conductive particles can be embedded in the fiber to prepare a durable conductive fiber (CN87104346A), or the conventional fiber can be scoured in a metal ion melt to prepare a durable conductive fiber, but the conductive property is obtained. Both are poor.
  • Conductive particles adhered to the surface of conventional chemical fibers or fabrics (CN1424455A, CN1687511A, US6703123, US4716055, US4061827, etc.) have poor electrical conductivity.
  • the conductivity of the widely used carbon black coated organic conductive fiber is about 10 -5W -1 cm 1 (the lowest value of >10 -8W -i C m -i conductive fiber), but the conductive layer is damaged in the later weaving process. .
  • An object of the present invention is to provide a coaxial conductive elastic composite filament and a preparation method thereof for providing a coaxial conductive elastic composite filament having excellent electrical conductivity, good elasticity, large deformation amount, and shielding function.
  • a coaxial conductive elastic composite filament comprising a conductive layer having a coaxial structure, a shielding layer and an insulating layer, wherein the conductive layer is disposed at a center of the composite filament, and the insulating layer is disposed on the composite filament
  • An outer layer, the shielding layer is continuously disposed inside the insulating layer and is not in contact with the conductive layer, the conductive layer is composed of conductive particles and an elastic polymer matrix, and the insulating layer is composed of an elastic polymer.
  • the shielding layer is composed of conductive metal particles and an elastic polymer matrix.
  • the weight ratio of the components is: the conductive layer accounts for 30-60 parts, the shielding layer accounts for 5-10 parts, and the rest is the weight specific gravity of the insulating layer.
  • the elastic polymer matrix is an elastic polyurethane-based polymer.
  • the conductive particles are one or a combination of two or more of carbon black, graphite, and graphene.
  • the conductive metal particles are one of nano silver-based, nickel-based, and copper-based particles.
  • the conductive layer contains 50 ⁇ 3 ⁇ 4 ⁇ 90 ⁇ 3 ⁇ 4 W t ⁇ 3 ⁇ 4 in the conductive layer, and the conductive layer contains 70 ⁇ 3 ⁇ 4 ⁇ 90 ⁇ 3 ⁇ 4 ⁇ in the shielding layer.
  • Metal particles Preferably, the conductive layer contains 50 ⁇ 3 ⁇ 4 ⁇ 90 ⁇ 3 ⁇ 4 W t ⁇ 3 ⁇ 4 in the conductive layer, and the conductive layer contains 70 ⁇ 3 ⁇ 4 ⁇ 90 ⁇ 3 ⁇ 4 ⁇ in the shielding layer. Metal particles.
  • the present invention also provides a preparation method for preparing the coaxial conductive elastic composite filament as described above, the preparation method comprising the following steps:
  • Step S1 dispersing the conductive particles in the elastic polymer melt, and dispersing by ultrasonication to obtain a conductive layer melt;
  • Step S2 dispersing the conductive metal particles in the elastic polymer melt and dispersing by ultrasonication to obtain a shield layer melt;
  • Step S3 extruding the conductive layer melt, the elastic polymer melt, and the shielding layer melt by using the first screw, the second screw, and the third screw to be extruded into the coaxial composite orifice of the spinneret.
  • the three are composited and solidified into a wire to form a conductive layer, a shielding layer and an insulating layer of a coaxial structure, wherein the conductive layer is disposed at the center of the composite filament, and the insulating layer is disposed on the outer layer of the composite filament, shielding
  • the layer is continuously disposed inside the insulating layer and is not in contact with the conductive layer.
  • the extrusion rates of the first screw, the second screw, and the third screw are the same.
  • the ultrasonic frequency for ultrasonic dispersion is 40 to 53 ⁇ , and the power is 50 to 300 W.
  • the elastic conductive composite filament has a volume conductivity of 10 -6 to 10 2 W -icm -i, and an elongation at break is SOO ⁇ IOOO ⁇
  • Embodiments of the present invention have the following beneficial effects: According to the method for preparing a conductive elastic composite filament provided by the present invention, a concentric circular composite spinning technique is realized by using a three-screw technology, and the obtained elastic composite filament comprises three layers.
  • the composite filament having high elasticity, high electrical conductivity and shielding effect can be obtained by simple steps and low cost, and the filament can be woven into the wearable fabric to realize the electronic sensing device. Used in tight fabrics.
  • FIG. 1 is a schematic cross-sectional structural view of a coaxial conductive elastic composite filament prepared according to an embodiment of the present invention.
  • FIG. 2 is a scanning electron micrograph of a coaxial conductive elastic composite filament prepared according to an embodiment of the present invention.
  • FIG 3 is a cross-sectional view showing a composite orifice of a coaxial conductive elastic composite filament prepared according to an embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional structural view of a coaxial conductive elastic composite filament prepared according to an embodiment of the present invention.
  • 2 is a scanning electron micrograph of a coaxial conductive elastic composite filament prepared according to an embodiment of the present invention. As shown in FIG. 1 and FIG.
  • the coaxial conductive elastic composite filament comprises a shield layer 2 and an insulating layer 3 having a coaxial structure, wherein the conductive layer 1 is disposed at the center of the composite filament, and the insulating layer 3 is disposed at The outer layer of the composite filament, the shielding layer 2 is continuously disposed inside the insulating layer 3 and is not in contact with the conductive layer 1, the conductive layer 1 is composed of conductive particles and an elastic polymer matrix, and the insulating layer 3 is composed of an elastic polymer, the shielding layer 2 It consists of conductive metal particles and an elastomeric polymer matrix.
  • the shielding layer 2 is disposed inside the insulating layer 3 and has a continuous ring shape.
  • the shielding layer 2 may be continuously disposed inside the insulating layer 3 in other shapes.
  • the function of shielding is not limited to the present invention.
  • the conductive layer 1 is disposed in a composite The shaft portion of the filament, the insulating layer 3 is an outer ring structure wrapped around the outer surface of the conductive layer 1, and the shielding layer 2 is a thin electromagnetic shielding layer embedded in the inner portion of the insulating layer 3.
  • the conductive layer occupies 50% of the cross-sectional area, the insulating layer occupies SO ⁇ , and the shielding layer accounts for lO ⁇ Oy ⁇
  • the conductive particles containing SOy ⁇ in the conductive layer 1, that is, the weight ratio of the conductive particles to the elastic polymer matrix are: Conductive particles: The elastic polymer matrix is 1:1 ⁇ 9: 1.
  • the shielding layer 2 contains conductive metal particles of 70 ⁇ 3 ⁇ 4 ⁇ 90 ⁇ 3 ⁇ 4 W t ⁇ 3 ⁇ 4, that is, the weight ratio of the conductive metal particles to the elastic polymer matrix is: conductive metal particles: elastic polymer
  • the substrate is 7:3 ⁇ 9:1.
  • the weight ratio of each component is: conductive layer 1 accounts for 30 to 60 parts, shielding layer 2 accounts for 5 to 10 parts, and the rest is insulating layer 3 Weight specific gravity.
  • the weight ratio of each component is a conductive layer: shielding layer: the insulating layer is 5:1:4.
  • the weight ratio of each component is a conductive layer: shielding layer: insulating layer is 6:1:3
  • the elastic polymer matrix is an elastic polyurethane-based polymer.
  • the conductive particles are one or a combination of two or more of carbon black, graphite, and graphene.
  • the conductive particles are 70% by weight of carbon nanorods.
  • the conductive particles are 60% by weight of graphene particles.
  • the conductive metal particles are one or a combination of two or more of nano silver-based, nickel-based, and copper-based particles.
  • the conductive metal particles are 70% by weight of nickel-based particles (having an average particle diameter of 500 nm).
  • the conductive metal particles are copper particles (average particle diameter of 500 nm) of 70 ⁇ 3 ⁇ 4 wt ⁇ 3 ⁇ 4.
  • Step S1 dispersing the conductive particles in the elastic polymer melt, and uniformly dispersing by ultrasonication to obtain a conductive layer melt;
  • conductive particles of 50 ⁇ 3 ⁇ 4 to 90 ⁇ 3 ⁇ 4 W t ⁇ 3 ⁇ 4 are dispersed in a polyurethane-based polymer melt, and uniformly dispersed by ultrasonic for 2 to 10 minutes to obtain a conductive layer melt.
  • Step S2 dispersing the conductive metal particles in the elastic polymer melt and uniformly dispersing by ultrasonication
  • the conductive metal particles of 70 ⁇ 3 ⁇ 4 ⁇ 90 ⁇ 3 ⁇ 4 W t ⁇ 3 ⁇ 4 are dissolved in the polyurethane-based polymer melt, and uniformly dispersed by ultrasonic for 2 to 5 minutes to obtain a shield layer melt.
  • Step S3 extruding the conductive layer melt, the elastic polymer melt, and the shielding layer melt by using the first screw, the second screw, and the third screw to be introduced into the coaxial composite orifice of the spinneret , the three are composited and solidified into a wire to form a conductive layer, a shielding layer and an insulating layer of a coaxial structure, wherein the conductive layer is disposed at the center of the composite filament, and the insulating layer is disposed on the outer layer of the composite filament, shielding The layer is continuously disposed inside the insulating layer and is not in contact with the conductive layer.
  • the ultrasonic frequency for ultrasonic dispersion is 40 to 53 KHZ, and the power is 50 to 300 W.
  • the ultrasonic frequency is 50 kHz and the power is 200 watts.
  • the volume conductivity of the elastic conductive composite filament is lO ⁇ KPW 'cm -i , and the elongation at break is SOOHOOO ⁇
  • the carbon nanorods are dispersed in the polyurethane polymer melt, dispersed by ultrasonic for 10 minutes, the ultrasonic frequency is 50 ⁇ , and the power is 200 W, so that the carbon nanorod particles are uniformly distributed in the polyurethane polymer melting.
  • the dispersed melt is extruded into the center hole of the spinneret by the first screw and extruded as a central conductive layer; and the polyurethane-based polymer melt is extruded as a conductive material on the outer side of the central conductive layer by the second screw.
  • the insulating coating of the layer, the polyurethane of the insulating layer and the polyurethane in the conductive layer have the same molecular weight; the nickel-based particles (having an average particle diameter of 500 nm) 70% by weight, dispersed in the polyurethane-based polymer melt, passed through the ultrasonic The dispersion was carried out for 10 minutes, and the ultrasonic frequency was 50 kHz, so that the nickel-based particles were uniformly distributed in the urethane-based polymer melt, and the dispersed melt was extruded into the spinneret by extrusion with a third screw placed in the middle of the elastic insulating layer.
  • a conductive layer, a shielding layer and an insulating layer of a coaxial structure are formed, wherein the conductive layer accounts for 50 parts 50, the shielding layer accounts for 10 parts, the insulating layer accounts for 40 parts, and the volume conductivity of the elastic conductive composite filaments is 10%.
  • ⁇ W -'cm -i elongation at break up to 1000%.
  • the first screw, the second screw and the third screw have the same extrusion rate to ensure the same stretching rate and structural uniformity.
  • the melt serves as an insulating coating layer of the conductive layer, and the polyurethane of the insulating layer and the polyurethane layer of the conductive layer have the same molecular weight; the copper-based particles (having an average particle diameter of 500 nm) 70% by weight are dispersed in the polyurethane-based polymer to be melted In the liquid, it is dispersed by ultrasonic for 10 minutes, the ultrasonic frequency is 50KHz, and the power is 200W, so that the copper-based particles are evenly distributed in the polyurethane-based polymer melt, and the dispersed melt is utilized in the third screw placed in the middle of the elastic insulating layer. Extrusion is introduced into the spinneret for extrusion.
  • a conductive layer, a shielding layer and an insulating layer of a coaxial structure are formed, wherein the conductive layer accounts for 60 parts, the shielding layer accounts for 10 parts, the insulating layer accounts for 30 parts, and the volume conductivity of the elastic conductive composite filaments is 10 - 3 W cm - 1 , elongation at break up to 800%.
  • the extrusion rates of the first screw, the second screw and the third screw are the same to ensure the same stretching rate and structural uniformity.
  • the method for preparing a conductive elastic composite filament provided by the present invention, a concentric circular composite spinning technique is realized by a three-screw technology, and the obtained elastic composite filament comprises a three-layer structure, wherein the conductive layer is a shaft of the composite fiber.
  • the insulating layer is an outer annular structure, which contains a very thin electromagnetic shielding layer in the insulating layer, and the three-layer structure is based on elastic polyurethane.
  • the composite filament having high elasticity, high electrical conductivity and shielding effect can be obtained by simple steps and low cost, and the filament can be woven into the wearable fabric to realize the electronic sensing device. Used in tight fabrics.

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Abstract

一种同轴导电弹性复合长丝及其制备方法，该长丝包括具有同轴结构的导电层（1）、屏蔽层（2）和绝缘层（3），绝缘层包裹在导电层外面，屏蔽层镶嵌于绝缘层内部，导电层由导电粒子和弹性聚合物基体组成，绝缘层由弹性聚合物组成，屏蔽层由导电金属颗粒和弹性聚合物基体组成。该制备方法利用三螺杆技术实现同心圆复合纺丝技术，所得到的弹性复合长丝包含三层结构，其中，导电层为复合纤维的轴部，绝缘层为外部环状结构，在绝缘层内含有一层很薄的电磁屏蔽层，且三层结构都以弹性聚氨酯为基体。由此，通过简单的步骤和较低的成本即可得到同时具有高弹性、高导电、屏蔽效果好的复合长丝，该长丝可编织到可穿戴面料中去，以实现电子传感设备在紧身面料中的使用。

Description

明名称：同轴导电弹性复合长丝及其制备方法 技术领域
[0001] 本发明涉及复合纤维技术领域， 尤其涉及一种具有优良导电性、 弹性好、 变形 量大且具有屏蔽功能的同轴导电弹性复合长丝及其制备方法。
背景技术
[0002] 研究表明， 我国正逐步进入"老年型"社会。 人口老齢化进程的加快以及各种慢 性病在中青年人群中有蔓延的趋势， 人们健康意识和保健要求日益增强， 所有 这一切都正在推动医疗模式从以症状治疗为中心向以预防为主、 早诊断、 早治 疗的模式转变。 将医疗服务 (如慢性病人监测和疾病康复医疗等)延伸到社区医生 和家庭医生， 这带来了家庭和社区医疗监护仪器的迅速发展。 可穿戴式的无线 医疗监护 (health care)仪是此类远程实吋监测的中心组件， 只要戴上轻巧腕表型 或其它可穿戴式医疗仪器， 居民在家里就可以利用高频率的无线多通道数据传 输方式， 把相关的人体生理信号如心电图 (ECG)、 血氧饱和度 (Sp0 2)和血压等数 据参数， 通过无线网络发送到医院监控中心， 监控中心接收信号后作出相应紧 急救护， 达到远程实吋监测的目的。 因此， 能够应用于准确探测生理信号变化 的可穿戴式医疗设备的衣物材料是重要的研究课题。
[0003] 金属丝具有良好的导电性能， 但是将其加入用于穿着的纺织品吋容易给人刺痒 感。 1974年美国杜邦公司采用复合纺丝技术成功制备出以炭黑为导电芯层的复 合有机聚合物导电纤维， 以用于抗静电纺织品及电磁屏蔽应用领域。 聚合物导 电纤维在穿戴纺织品中避免了因模量问题给人的不舒适感， 而且在导电通道内 可在外界刺激下能够快速可逆响应， 具有智能及多功能实吋监测的潜力， 加上 制备成本低， 编织性及耐洗磨好， 应用前景光明。
[0004] 复合纺丝技术可以把导电颗粒及常规聚合物分层制备。 例如将导电组分 （碳纳 米管、 炭黑等） 或含有导电组分的母粒与聚合物基体共混， 再进一步纺丝得到 导电纤维 （CN1569939A, CN1438363A, CN101158058A,
CN1584140A和 CN1563526A) 。 通常而言， 需要加入含量较高的导电粉末到物 理共混熔融液中， 来提高导电纤维的电学性能， 这不仅会使得纺丝熔体过滤性 变差， 纺丝困难， 还会导致纤维的力学性能大幅度下降。 而湿法纺丝制备的导 电纤维其电导率又偏低 （CN1450210A) ， 而后期的在纤维表面简单的涂层或者 沉积导电层， 在实际使用中导电效果又容易受外界干扰， 导电层也易脱落。 而 将纤维制备成大量微孔结构， 然后将导电颗粒嵌入纤维内部的方法可以制备耐 久性导电纤维 （CN87104346A) ， 或者利用常规纤维在金属离子熔融液中煮练 制备耐久导电纤维， 但其导电性能都较差。 常规化学纤维或面料表面黏附导电 粒子 (CN1424455A, CN1687511A, US6703123 , US4716055 , US4061827等） 其导电耐久性差。 目前应用较广的炭黑涂敷型有机导电纤维的电导率在 10 -5W -1 cm 1 (>10 -8W -iCm -i导电纤维最低值） 左右， 但后期编织过程有损坏导电层。
[0005] 实现导电纤维的弹性， 目前多利用复合技术， 例如在弹力丝的表面在纺纱工艺 中缠绕导电纤维 （US20080282665A1 , CN1813087B) ， 弹力纤维在拉伸吋， 宽 松缠绕的导电纤维也随之拉伸变形， 实现了弹性及导电的同吋性。 或者， 在常 规弹力丝的表面涂敷一层导电颗粒层 （CN102121192B) 。 但这些弹力导电丝没 有阐述拉伸吋对导电性能的影响， 另外， 该导电丝的对外界的屏蔽功能也没有 考虑。 因此在可穿戴电子设备中应用吋还具有局限性。
技术问题
[0006] 本发明的目的在于提供一种同轴导电弹性复合长丝及其制备方法以提供一种具 有优良导电性、 弹性好、 变形量大且具有屏蔽功能的同轴导电弹性复合长丝。 问题的解决方案
技术解决方案
[0007] 一种同轴导电弹性复合长丝， 包括具有同轴结构的导电层、 屏蔽层和绝缘层， 所述导电层设置在复合长丝的中心， 所述绝缘层设置在复合长丝的外层， 所述 屏蔽层连续设置于所述绝缘层内部呈且不与所述导电层接触， 所述导电层由导 电粒子和弹性聚合物基体组成， 所述绝缘层由弹性聚合物组成， 所述屏蔽层由 导电金属颗粒和弹性聚合物基体组成。
[0008] 优选地， 组分的重量配比为： 所述导电层占 30~60份， 所述屏蔽层占 5~10份， 其余部分为所述绝缘层的重量比重。 [0009] 优选地， 所述弹性聚合物基体为弹性聚氨酯类聚合物。
[0010] 优选地， 所述导电粒子为碳黑、 石墨、 石墨烯中的一种或两种以上的组合。
[0011] 优选地， 所述导电金属颗粒为纳米银系、 镍系、 铜系颗粒中的一种。
[0012] 优选地， 在所述导电层中含有 50<¾~90<¾Wt<¾的所述导电粒子， 在所述屏蔽层中 含有 70<¾~90<¾\ν^ 所述导电金属颗粒。
[0013] 相应地， 本发明还提供一种用于制备如上所述的同轴导电弹性复合长丝的制备 方法， 所述制备方法包括以下步骤：
[0014] 步骤 S1 : 将导电粒子分散于弹性聚合物熔融液中， 通过超声进行分散， 得到导 电层熔融液；
[0015] 步骤 S2: 将导电金属颗粒分散于弹性聚合物熔融液中， 通过超声进行分散， 得 到屏蔽层熔融液； 以及
[0016] 步骤 S3: 将导电层熔融液、 弹性聚合物熔融液和屏蔽层熔融液分别利用第一螺 杆、 第二螺杆和第三螺杆挤压导入喷丝板的同轴复合喷丝孔挤出， 使三者复合 成一体并凝固成丝， 形成同轴结构的导电层、 屏蔽层和绝缘层， 其中， 导电层 设置在复合长丝的中心， 绝缘层设置在复合长丝的外层， 屏蔽层连续设置于绝 缘层内部且不与导电层接触。
[0017] 优选地， 第一螺杆、 第二螺杆和第三螺杆的挤出速率相同。
[0018] 优选地， 用于超声分散的超声波频率为 40~53ΚΗΖ， 功率为 50~300W。
[0019] 优选地， 所述弹性导电复合长丝的体积电导率为 10 -6~10 2W -icm -i， 断裂伸长 率为 SOO^ IOOO^
发明的有益效果
有益效果
[0020] 实施本发明实施例， 具有如下有益效果： 根据本发明提供的导电弹性复合长丝 制备工艺方法， 利用三螺杆技术实现同心圆复合纺丝技术， 所得到的弹性复合 长丝包含三层结构， 其中， 导电层为复合纤维的轴部， 绝缘层为外部环状结构 ， 在绝缘层内含有一层很薄的电磁屏蔽层， 且三层结构都以弹性聚氨酯为基体 。 由此， 通过简单的步骤和较低的成本即可得到同吋具有高弹性、 高导电、 屏 蔽效果好的复合长丝， 该长丝可编织到可穿戴面料中去， 以实现电子传感设备 在紧身面料中的使用。
对附图的简要说明
附图说明
[0021] 为了更清楚地说明本发明实施例或现有技术中的技术方案， 下面将对实施例或 现有技术描述中所需要使用的附图作简单地介绍， 显而易见地， 下面描述中的 附图仅仅是本发明的一些实施例， 对于本领域普通技术人员来讲， 在不付出创 造性劳动的前提下， 还可以根据这些附图获得其他的附图。
[0022] 图 1为本发明一实施例制备的同轴导电弹性复合长丝的截面结构示意图。
[0023] 图 2为本发明一实施例制备的同轴导电弹性复合长丝的扫描电镜图。
[0024] 图 3为本发明一实施例制备的同轴导电弹性复合长丝吋使用的复合喷丝孔的截 面示意图。
[0025] 图中： 1-导电层； 2-屏蔽层； 3-绝缘层； 4-喷丝板上对应于导电层的通孔； [0026] 5-喷丝板上对应于绝缘层的通孔； 6-喷丝板上对应于屏蔽层的通孔。
实施该发明的最佳实施例
本发明的最佳实施方式
[0027] 下面将结合本发明实施例中的附图， 对本发明实施例中的技术方案进行清楚、 完整地描述， 显然， 所描述的实施例仅仅是本发明一部分实施例， 而不是全部 的实施例。 基于本发明中的实施例， 本领域普通技术人员在没有作出创造性劳 动前提下所获得的所有其他实施例， 都属于本发明保护的范围。
[0028] 图 1为本发明一实施例制备的同轴导电弹性复合长丝的截面结构示意图。 图 2为 本发明一实施例制备的同轴导电弹性复合长丝的扫描电镜图。 如图 1和图 2所示 ， 同轴导电弹性复合长丝包括具有同轴结构的 1、 屏蔽层 2和绝缘层 3， 其中， 导 电层 1设置在复合长丝的中心， 绝缘层 3设置在复合长丝的外层， 屏蔽层 2连续设 置于绝缘层 3内部且不与导电层 1接触， 导电层 1由导电粒子和弹性聚合物基体组 成， 绝缘层 3由弹性聚合物组成， 屏蔽层 2由导电金属颗粒和弹性聚合物基体组 成。 在本发明一实施例中， 屏蔽层 2设置于绝缘层 3内部且呈连续的环状， 本领 域技术人员应该理解的是， 屏蔽层 2也可以以其他的形状连续设置于绝缘层 3内 部以起到屏蔽的作用， 本发明并不以此为限。 更具体地， 导电层 1为设置在复合 长丝的轴部， 绝缘层 3为包裹在导电层 1外面的外层环状结构， 屏蔽层 2为镶嵌于 绝缘层 3的内部的一层很薄的电磁屏蔽层。 优选地， 在弹性复合长丝的横截面中 ， 导电层占横截面面积的 50%， 绝缘层占 SO^ ^, 而屏蔽层占 lO^ Oy^
[0029] 进一步地， 在导电层 1中含有 SOy^^^wt^的导电粒子， 即导电粒子与弹性聚 合物基体的重量配比为： 导电粒子： 弹性聚合物基体为 1:1~9:1。
[0030] 进一步地， 在屏蔽层 2中含有 70<¾~90<¾Wt<¾的导电金属颗粒， 即导电金属颗粒 与弹性聚合物基体的重量配比为： 导电金属颗粒： 弹性聚合物基体为 7:3~9:1。
[0031] 进一步地， 在同轴导电弹性复合长丝中， 各组分的重量配比为： 导电层 1占 30~ 60份， 屏蔽层 2占 5~10份， 其余部分为绝缘层 3的重量比重。 优选地， 在本发明 一实施例中， 各组分的重量配比为导电层： 屏蔽层： 绝缘层为 5:1:4。 优选地， 在本发明另一实施例中， 各组分的重量配比为导电层： 屏蔽层： 绝缘层为 6:1:3
[0032] 进一步地， 弹性聚合物基体为弹性聚氨酯类聚合物。
[0033] 进一步地， 导电粒子为碳黑、 石墨、 石墨烯中的一种或两种以上的组合。 优选 地， 在本发明一实施例中， 在导电层中， 导电粒子为 70%wt%的碳纳米棒。 优选 地， 在本发明另一实施例中， 在导电层中， 导电粒子为 60%\^%的石墨烯粒子。
[0034] 进一步地， 导电金属颗粒为纳米银系、 镍系、 铜系颗粒中的一种或两种以上的 组合。 优选地， 在本发明一实施例中， 在屏蔽层中， 导电金属颗粒为 70%\^%的 镍系颗粒 （平均粒径为 500nm) 。 优选地， 在本发明另一实施例中， 在屏蔽层中 ， 导电金属颗粒为 70<¾wt<¾的铜系颗粒 （平均粒径为 500nm) 。
[0035] 在本发明的另一实施例中， 提供了一种制备如上所述的同轴导电弹性复合长丝 的制备方法， 包括以下步骤：
[0036] 步骤 S1 : 将导电粒子分散于弹性聚合物熔融液中， 通过超声进行均匀分散， 得 到导电层熔融液；
[0037] 具体地， 将 50<¾~90<¾Wt<¾的导电粒子分散于聚氨酯类聚合物熔融液中， 通过超 声均匀分散 2~10分钟， 得到导电层熔融液。
[0038] 步骤 S2: 将导电金属颗粒分散于弹性聚合物熔融液中， 通过超声进行均匀分散
， 得到屏蔽层熔融液； [0039] 具体地， 将 70<¾~90<¾Wt<¾的导电金属颗粒溶于聚氨酯类聚合物熔融液中， 通过 超声均匀分散 2~5分钟， 得到屏蔽层熔融液。
[0040] 步骤 S3: 将导电层熔融液、 弹性聚合物熔融液和屏蔽层熔融液分别利用第一螺 杆、 第二螺杆和第三螺杆挤压导入喷丝板的同轴复合喷丝孔挤出， 使三者复合 成一体并凝固成丝， 形成同轴结构的导电层、 屏蔽层和绝缘层， 其中， 导电层 设置在复合长丝的中心， 绝缘层设置在复合长丝的外层， 屏蔽层连续设置于绝 缘层内部且不与导电层接触。
[0041] 进一步地， 第一螺杆、 第二螺杆和第三螺杆的挤出速率相同。
[0042] 进一步地， 用于超声分散的超声波频率为 40~53KHZ， 功率为 50~300W。 优选 地， 在本发明一实施例中， 超声波频率 50KHz， 功率为 200W。
[0043] 进一步地， 弹性导电复合长丝的体积电导率为 lO ^KPW 'cm -i , 断裂伸长率 为 SOOHOOO^
[0044] 实施例 1
[0045] 将碳纳米棒 70%wt%， 分散于聚氨酯类聚合物熔融液中， 通过超声分散 10分钟 ， 超声波频率为 50ΚΗζ， 功率为 200W， 使得碳纳米棒颗粒均匀分布于聚氨酯类 聚合物熔融液中， 将分散后的熔融液利用第一螺杆挤压导入喷丝板的中心孔， 作为中心导电层挤出； 在中心导电层的外侧利用第二螺杆挤出聚氨酯类聚合物 熔融液作为导电层的绝缘包覆层， 该绝缘层的聚氨酯和导电层中聚氨酯具有相 同的分子量； 将镍系颗粒 （粒径平均为 500nm) 70%wt%, 分散于聚氨酯类聚合 物熔融液中， 通过超声分散 10分钟， 超声波频率为 50KHz， 使得镍系颗粒均匀分 布于聚氨酯类聚合物熔融液中， 将分散后的熔融液利用放置于弹性绝缘层中间 的第三螺杆挤压导入喷丝板挤出。 由此， 形成同轴结构的导电层、 屏蔽层和绝 缘层， 其中， 导电层占 50份 50， 屏蔽层占 10份， 绝缘层占 40份， 且弹性导电复 合长丝的体积电导率为 lO ^W -'cm -i , 断裂伸长率可达 1000%。 第一螺杆、 第二 螺杆和第三螺杆的挤出速率相同， 以保证相同拉伸速率及结构均匀性。
[0046] 实施例 2
[0047] 将石墨烯粒子 60%wt%， 分散于聚氨酯类聚合物熔融液中， 通过超声分散 10分 钟， 超声波频率为 50KHz， 功率为 200W， 使得碳纳米棒颗粒均匀分布于聚氨酯 类聚合物熔融液中， 将分散后的熔融液利用第一螺杆挤压导入喷丝板的中心孔 ， 作为中心导电层挤出； 在中心导电层的外侧利用第二螺杆挤出聚氨酯类聚合 物熔融液作为导电层的绝缘包覆层， 该绝缘层的聚氨酯和导电层中聚氨酯一具 有相同的分子量； 将铜系颗粒 （粒径平均为 500nm) 70%wt% , 分散于聚氨酯类 聚合物熔融液中， 通过超声分散 10分钟， 超声波频率为 50KHz,功率为 200W， 使 得铜系颗粒均匀分布于聚氨酯类聚合物熔融液中， 将分散后的熔融液利用放置 于弹性绝缘层中间的第三螺杆挤压导入喷丝板挤出。 由此， 形成同轴结构的导 电层、 屏蔽层和绝缘层， 其中， 导电层占 60份， 屏蔽层占 10份， 绝缘层占 30份 ， 且弹性导电复合长丝的体积电导率为 10 -3W cm -1 , 断裂伸长率可达 800%。 第 一螺杆、 第二螺杆和第三螺杆的挤出速率相同， 以保证相同拉伸速率及结构均 匀性。
[0048] 根据本发明提供的导电弹性复合长丝制备工艺方法， 利用三螺杆技术实现同心 圆复合纺丝技术， 所得到的弹性复合长丝包含三层结构， 其中， 导电层为复合 纤维的轴部， 绝缘层为外部环状结构， 在绝缘层内含有一层很薄的电磁屏蔽层 ， 且三层结构都以弹性聚氨酯为基体。 由此， 通过简单的步骤和较低的成本即 可得到同吋具有高弹性、 高导电、 屏蔽效果好的复合长丝， 该长丝可编织到可 穿戴面料中去， 以实现电子传感设备在紧身面料中的使用。
[0049] 以上所揭露的仅为本发明一种较佳实施例而已， 当然不能以此来限定本发明之 权利范围， 本领域普通技术人员可以理解实现上述实施例的全部或部分流程， 并依本发明权利要求所作的等同变化， 仍属于发明所涵盖的范围。

Claims

权利要求书
一种同轴导电弹性复合长丝， 其特征在于， 包括具有同轴结构的导电 层、 屏蔽层和绝缘层， 所述导电层设置在复合长丝的中心， 所述绝缘 层设置在复合长丝的外层， 所述屏蔽层连续设置于所述绝缘层内部且 不与所述导电层接触， 所述导电层由导电粒子和弹性聚合物基体组成 ， 所述绝缘层由弹性聚合物组成， 所述屏蔽层由导电金属颗粒和弹性 聚合物基体组成。
根据权利要求 1所述的同轴导电弹性复合长丝， 其特征在于， 各组分 的重量配比为： 所述导电层占 30~60份， 所述屏蔽层占 5~10份， 其余 部分为所述绝缘层的重量比重。
根据权利要求 1所述的同轴导电弹性复合长丝， 其特征在于， 所述弹 性聚合物基体为聚氨酯类聚合物。
根据权利要求 1所述的同轴导电弹性复合长丝， 其特征在于， 所述导 电粒子为碳黑、 石墨、 石墨烯中的一种或两种以上的组合。
根据权利要求 1所述的同轴导电弹性复合长丝， 其特征在于， 所述导 电金属颗粒为纳米银系、 镍系、 铜系颗粒中的一种或两种以上的组合
[权利要求 6] 根据权利要求 1所述的同轴导电弹性复合长丝， 其特征在于， 在所述 导电层中含有 50<¾~90<¾Wt<¾的所述导电粒子， 在所述屏蔽层中含有 70 y^QO^wt^^ 所述导电金属颗粒。
[权利要求 7] —种用于制备如权利要求 1-6所述的同轴导电弹性复合长丝的制备方 法， 其特征在于， 所述制备方法包括以下步骤：
步骤 S1 : 将导电粒子分散于弹性聚合物熔融液中， 通过超声进行分散 ， 得到导电层熔融液；
步骤 S2: 将导电金属颗粒分散于弹性聚合物熔融液中， 通过超声进行 分散， 得到屏蔽层熔融液； 以及
步骤 S3: 将导电层熔融液、 弹性聚合物熔融液和屏蔽层熔融液分别利 用第一螺杆、 第二螺杆和第三螺杆挤压导入喷丝板的同轴复合喷丝孔 挤出， 使三者复合成一体并凝固成丝， 形成同轴结构的导电层、 屏蔽 层和绝缘层， 其中， 导电层设置在复合长丝的中心， 绝缘层设置在复 合长丝的外层， 屏蔽层连续设置于绝缘层内部且不与导电层接触。
[权利要求 8] 根据权利要求 7所述的同轴导电弹性复合长丝的制备方法， 其特征在 于， 第一螺杆、 第二螺杆和第三螺杆的挤出速率相同。
[权利要求 9] 根据权利要求 7所述的同轴导电弹性复合长丝的制备方法， 其特征在 于， 用于超声分散的超声波频率为 40~53KHZ， 功率为 50~300W。
[权利要求 10] 根据权利要求 7所述的同轴导电弹性复合长丝的制备方法， 其特征在 于， 所述弹性导电复合长丝的体积电导率为 lO K W ^m -i , 断裂 伸长率为 oo^ ioooy^
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