CN107614783B - 电导性织物元件及其制备方法 - Google Patents
电导性织物元件及其制备方法 Download PDFInfo
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- CN107614783B CN107614783B CN201680013354.7A CN201680013354A CN107614783B CN 107614783 B CN107614783 B CN 107614783B CN 201680013354 A CN201680013354 A CN 201680013354A CN 107614783 B CN107614783 B CN 107614783B
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- textile element
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Abstract
本发明提供了一种电导性织物元件及其制备方法。所述方法包括如下步骤：(i)用带负电的聚电解质对织物元件的表面进行改性；和(ii)用金属粒子涂布织物元件的改性过的表面。
Description
技术领域
本发明涉及电导性织物元件和其生产方法领域。
背景技术
随着柔性并且耐磨的电子器件的快速进步，需要可以整合到电导性织物/服装中的作为互连、触点、电极和金属线的导体。因此，已经开发了合成生产高性能电导性织物的方法，其包括通过金属线、金属氧化物、本征电导性聚合物(ICP)和碳纳米管(CNT)合成纱线或合成并有金属线、金属氧化物、固有电导性聚合物(ICP)和碳纳米管(CNT)的纱线。然而，根据这些现有方法生产的电导性织物由于以下原因而不理想：其非柔性、化学不稳定性、生产成本、对人体的危害，以及最显著地，与用当前织物和服装行业的相容技术大规模制备有关的困难。
合成电导性织物的另一种方法包括使用各种金属粒子沉积技术将金属涂层沉积到织物衬底表面上。然而，在如下方面还存在与这种方法有关的限制：对所涉及的技术、先进的仪器装备和专业的劳动力专业技术的相对投资量，以及需要相对精确的控制参数，其限制了这种工艺在商业上进行工业化。此外，沉积金属在织物表面上的粘附性仍然是关于这些电导性织物的耐久性和电导性性的另一个主要关心问题。
已经开发了涉及通过将官能化的聚合物刷接枝在织物衬底的表面架构上来使其改性的其它工艺。具体地，将一端共价拴系在织物衬底表面上的聚电解质不仅在织物衬底表面上提供改性的官能团，而且增加了用于后续化学反应中的官能团的量。举例来说，Azzaroni等人展示了将带正电的聚氯化[2-(甲基丙烯酰氧基)乙基]三甲基铵(PMETAC)聚电解质接枝到衬底表面上。在装载催化部分四氯钯酸根(II)阴离子([PdCl4]2-)来进行后续金属无电沉积(ELD)的情况下，能够选择性地沉积具有适合的粘附特性的坚固金属层。在2010年，Liu等人报道了一种制备耐久的电导性棉纱的通用方法，其也是通过使用表面引发的原子转移自由基聚合(SI-ATRP)在棉纤维表面上生长PMETAC刷来进行，这是第一次展示在天然织物纤维上接枝PMETAC刷。后续的金属ELD产生具有高电稳定性的电导性棉纱，其能够经受多次弯曲、拉伸、摩擦和甚至洗涤循环。然而，Liu等人讲授的SI-ATRP方法的规模生产的可行性遭受了各种问题。例如，SI-ATRP不能在环境条件下适当地进行并且需要氮气保护。此外，SI-ATRP反应涉及相对长时间(约24小时)，这对于大量生产来说不适宜并且并非成本有效的。因此，需要改良合成工艺来允许高通量的电导性织物生产。
已经进行其它尝试来改良合成方法，其通过在各种织物衬底上沉积金属来制备电导性纤维、纱线和织品进行，所述各种织物衬底预先用相同的带正电的聚电解质PMETAC使用原位自由基聚合改性。原位自由基聚合可以提高聚电解质聚合的通量。一般来说，该反应仅耗费约1-3小时来完成，并且可以在环境条件下进行，相对于其它聚合方法(如前述SI-ATRP)，其非常有利。然而，这种改良方法具有如下缺陷：因为催化部分的选择高度取决于接枝在织物表面上的聚电解质刷的特性和性质，所以阳离子PMETAC只限于与阴离子[PdCl4]2-部分偶合来进行后续无电金属沉积。此外，所用[PdCl4]2-部分相对昂贵(每2克97％的四氯钯酸(II)铵，USD159.5)。即使阴离子[PdCl4]2-部分可以再使用，但如果将其用于大量生产，其仍然是不经济的。
发明内容
本发明试图减轻上述问题中的至少一种。
本发明可涉及数种广泛形式。本发明的实施方式可以包括本文描述的不同广泛形式中的一种或任何组合。
在第一广泛形式中，本发明提供一种生产电导性织物元件的方法，其包括如下步骤：
(i)用带负电的聚电解质对织物元件的表面进行改性；和
(ii)用金属粒子涂布织物元件的改性过的表面。
优选地，步骤(i)可以包括用带负电的聚电解质通过原位自由基聚合对织物元件的表面进行改性。
优选地，带负电的聚电解质可以包括聚(甲基丙烯酸钠盐)和聚(丙烯酸钠盐)中的至少一种。
优选地，步骤(i)可以包括用带负电的聚电解质对织物元件的硅烷化表面进行改性。
优选地，步骤(ii)可以包括用金属粒子通过无电金属沉积涂布织物元件的改性过的表面。
优选地，金属粒子可以包括铜和镍粒子中的至少一种。
优选地，织物元件可以包括被配置来形成织品的纱线和纤维中的至少一种。
优选地，织物元件可以包括聚酯、尼龙、棉和丝线或纤维中的至少一种。
在另一个广泛形式中，本发明提供一种用于生产电导性织物元件的装置，其包括：
用于用带负电的聚电解质对织物元件的表面进行改性的装置；和
用于用金属粒子涂布织物元件的改性过的表面的涂布装置。
优选地，用于用带负电的聚电解质对织物元件的表面进行改性的装置可以被配置成用带负电的聚电解质通过原位自由基聚合对织物元件的表面进行改性。
优选地，带负电的聚电解质可以包括聚(甲基丙烯酸钠盐)和聚(丙烯酸钠盐)中的至少一种。
优选地，用于用带负电的聚电解质对织物元件的表面进行改性的装置可以被配置成用带负电的聚电解质对织物元件的硅烷化表面进行改性。
优选地，涂布装置可以被配置成用金属粒子通过无电金属沉积涂布织物元件的改性过的表面。
优选地，金属粒子可以包括铜和镍粒子中的至少一种。
优选地，织物元件可以包括被配置来形成织品的纱线和纤维中的至少一种。
优选地，织物元件可以包括聚酯、尼龙、棉和丝线或纤维中的至少一种。
在另一个广泛形式中，本发明提供一种电导性织物元件，其根据本发明的第一广泛形式的方法步骤生产。
在另一个广泛形式中，本发明提供一种由至少一个织物元件形成的织品，其中所述至少一个织物元件根据本发明的第一广泛形式的方法步骤生产。
附图说明
将从结合附图描述的本发明的优选但非限制性实施方式的以下详细描述更充分地理解本发明，其中：
图1为根据本发明的一个实施方式通过原位自由基聚合制备电导性棉纱的工艺的示意图；
图2描绘根据图1中描绘的方法生产的示例性涂铜棉纱；
图3描绘关于根据本发明的一个实施方式形成的原始棉纱、硅烷改性棉和PMANa改性棉纱的傅里叶变换红外光谱学(FTIR)光谱数据的表现；
图4描绘根据本发明的一个实施方式生产的PMANa改性棉的EDX光谱的表现；
图5描绘表示具有不同改性的棉纤维的表面形态的SEM影像，所述棉纤维包括(A)原始棉；(B)硅烷改性棉；(C)PMANa涂布棉；(D-F)根据本发明一个实施方式的涂铜棉；
图6描绘表示以下参数的数据：(A)如此合成的涂铜棉纱的线性电阻，和(B)根据本发明一个实施方式生产的棉纱的拉伸强度；
图7描绘用于生产由根据本发明一个实施方式生产的涂铜纱线形成的编织品的工艺步骤；
图8描绘从根据本发明一个实施方式生产的涂铜纱线编织的织品的薄层电阻数据；
图9描绘从在不同洗涤次数下洗涤的织品解开的棉纱的SEM影像，所述棉纱根据本发明一个实施方式生产；
图10描绘根据本发明一个实施方式生产的PMANa辅助的涂镍棉织品；
图11A描绘根据本发明一个实施方式形成的示例性的PAANa辅助的涂铜纱线；
图11B描绘根据本发明一个实施方式形成的示例性的PAANa辅助的涂镍丝线；
图12A描绘根据本发明一个实施方式生产的PAANa辅助的涂铜尼龙纱；并且
图12B描绘由根据本发明一个实施方式生产的PAANa辅助的涂铜尼龙纱形成的聚酯织品。
具体实施方式
现在参考图1至图12B描述本发明的示例性实施方式。
首先参考图1，示意性说明在织物衬底(如棉纱)上制备PMANa聚电解质的程序。该实施方式涉及原位自由基聚合方法，其可以在棉纱上进行例如来制备涂聚(甲基丙烯酸钠盐)(PMANa)棉纱。接着可以进行后续离子交换、离子还原和在涂PMANa棉纱上无电沉积金属粒子以便产生具有适用于工业规模生产的质量的电导性棉纱。应该注意到，这个实施方式也可以适用于在织物衬底上制备PAANa聚电解质。
在执行该工艺时，首先将棉纱浸入5-20％(v/v)具有C＝C键的硅烷的溶液中约30分钟以便使纤维素的羟基与硅烷分子适当地反应。接着用新鲜的去离子(DI)水充分冲洗棉纱以便去除任何过量的物理吸附的硅烷和副产物分子。这个硅烷化步骤由图1中的(100)表示。
接着将冲洗的棉纱置放在烘箱中100-120℃下约15-30分钟来完成缩合反应。接着，将硅烷改性棉纱浸入约50mL包含3-7g MANa粉末和35-75mg K2S2O8的水溶液中(类似地，在PAANa聚电解质的情况下可以使用AANa粉末)。将含有棉纱的整个溶液混合物在60-80℃下在烘箱中加热0.5-1小时以便进行自由基聚合。在自由基聚合过程中，硅烷的双键可以被自由基打开，从而在棉纤维表面上生长PMANa聚电解质。这个自由基聚合步骤由图1中的(110)表示。
之后，将涂PMANa棉纱浸入39g/L五水合硫酸铜(II)溶液中0.5～1小时，其中Cu2+离子通过离子交换固定在聚合物上。继而在0.1-1.0M硼氢化钠溶液中还原，Cu2+被还原为Cu粒子，其充当用于在后续Cu的无电沉积中生长Cu的成核位置。这个离子交换和还原步骤由图1中的(120)表示。
将涂有聚合物的棉在于硼氢化钠溶液中还原后浸入由12g/L氢氧化钠、13g/L五水合硫酸铜(II)、29g/L酒石酸钠钾和9.5mL/L甲醛在水中的溶液组成的无电镀铜浴中60-180分钟。用去离子(DI)水冲洗如此合成的涂Cu纱线并且吹干。进行无电金属沉积的步骤由图1中的(130)表示，并且根据这个第一实施方式的方法步骤生产的示例性涂Cu棉纱由图2中的(200)表示。
硅烷改性棉和PMANa接枝棉能够用傅里叶变换红外光谱学(FTIR)表征。如图3所示，位于1602和1410cm-1的额外峰的存在表示硅烷分子中的C＝C键。位于769cm-1的另一个独特的峰归于Si-O-Si对称拉伸，指示棉纤维表面上硅烷分子成功地彼此交联。对于PMANa改性棉样品，表示羧酸盐不对称拉伸振动的位于1549cm-1的新峰证实PMANa接枝。位于1455和1411cm-1的其它峰都归于羧酸盐从PMANa的对称拉伸振动。
PMANa接枝棉也能够通过能量色散X射线光谱学(EDX)表征。图4中显示MANa聚合使棉样品具有钠元素，从而指示存在PMANa。再参考图5扫描电子显微术(SEM)影像，硅烷化棉纤维表面与原棉纤维表面的表面形态之间未明显看到显著差异。然而，在硅烷化棉纤维表面上聚合PMANa后，应注意在棉纤维表面上已包裹一层涂层。图5D-F显示铜金属粒子相对均匀地沉积，无任何裂缝迹象。
涂铜棉纱的电导性性能够用两探头电测试法表征。在这个方面，如图6A所示，发现生产中的涂铜纱线的线性电阻为约1.4Ω/cm，并且与未处理的棉纱相比具有优越的拉伸特性，如图6B所示，拉伸延伸(+33.6％)和最大负荷(+27.3％)两者都增加了。发觉拉伸延伸和最大负荷的增加是因为铜层对棉纱强度的加强。
为了进一步测试棉纱表面上铜的粘附性和洗涤耐久性，首先将涂铜棉纱编织成织品。首先通过使用工业纱线缠绕机将图7A中所示的如此合成的涂铜棉纱缠绕在图7B所示的锥体上。之后，将锥体转移到图7C所示的CCI织机，通过该织机将涂铜纱线编织成织品。在编织环境下，涂铜棉纱被配置成形成织品的纬纱，而织品的经纱用最初安装在织机上的如图7D的插入影像所示的未处理棉纱形成。编织工艺中未发现问题或缺陷。编织后，将织品切割成5cm×15cm的片，并且如图7D所示在四个边缘包缝，接着在以下洗涤条件下根据如下测试标准AATCC测试法61-测试第2A号进行一系列洗涤循环：洗涤色牢度，家用及商用：加速(机洗)(Colorfastness to Laundering,Home and Commercial:Accelerated(MachineWash))(图7E)：
| 洗涤温度 | 49±2℃ |
| DI水的体积 | 150mL |
| 添加的钢球数目 | 50pcs |
| 洗涤时间 | 45分钟 |
应该注意到，根据测试标准，1个洗涤循环等效于约5个商购机器洗涤循环。总共进行6个洗涤循环，因此，其被认为等效于约30个商购机器洗涤循环。能够使用四探头法评价洗涤的织品的电阻变化，如图8所示，通过该方法测定根据此实施方式生产的织品的薄层电阻为0.9±0.2Ω/sq(未洗涤)，在等效于约20个商购机器洗涤循环的第四次洗涤后为73.8±13.4Ω/sq。
洗涤的涂铜棉纱的表面形态能够通过从织品解开洗涤的涂铜棉纱并且在SEM下检查来表征。如图9的SEM影像所示，明显看到铜金属粒子保持在棉纤维的表面上。薄层电阻增加的一个发觉的原因是由于重复的洗涤循环，棉纤维的结构变松散。
还注意到，在向所生产的织品施加标准洗涤循环期间，向洗涤筒中添加50个钢球来试图模拟洗涤机有力的摩擦和拉伸力。钢球对织品的磨损基本上作用于纤维结构。因为涂铜棉纤维不再以紧密方式保持在一起，所以发觉其彼此丧失接触以便减少用于电子运动的电导性路径。因此，尽管在重复的洗涤循环后薄层电阻增加，但图9的SEM影像证实铜金属粒子相对强地粘附在棉纤维表面上。
在本发明的替代性实施方式中，不用铜粒子涂布棉纤维，而是可以替代地通过使用上述相同方法将镍金属粒子无电镀到织物表面上。可以进行相同的实验程序和测试，但可以在离子交换程序中使用的镍源为120g/L硫酸镍(II)溶液。接着，使用由40g/L六水合硫酸镍、20g/L柠檬酸钠、10g/L乳酸和1g/L二甲胺硼烷(DMAB)的水溶液组成的无电镀镍浴60-180分钟。如图8所示，发现所得涂镍棉织品的薄层电阻展现基本上与涂铜纤维纱线类似的结果。转向图10，示例性涂镍棉织品由(300)表示，其展现高度均匀的镍金属，其中体电阻测量为3.2Ω。
应了解，本发明的其它实施方式可以涉及使用除棉以外的衬底并且可以适当地被应用于各种织物材料，如丝、尼龙和聚酯。在这个方面，根据本发明一个实施方式生产的示例性PAANa辅助的涂铜纱线显示为由图11A中的(400)表示，根据本发明一个实施方式生产的示例性PAANa辅助的涂镍丝线显示为由图11B中的(500)表示，根据本发明一个实施方式生产的示例性PAANa辅助的涂铜尼龙纱显示为由图12A中的(600)表示，并且由根据本发明一个实施方式生产的PAANa辅助的涂铜尼龙纱形成的示例性聚酯织品由图12B中的(700)表示。
从本发明的广泛形式的前述概述可了解，可以方便地提供各种优势，包括可以生产可以具有适当柔性、耐磨性、耐久性和/或可洗涤性的电导性织物元件来整合到织物/织品中。此外，这些高性能电导性织物元件(纤维、纱线和织品)可以使用相对廉价的技术基于原位自由基聚合的化学反应成本有效地大规模生产来在织物衬底上生长带负电的聚电解质(如PMANa或PAANa)，从而可以方便地提供桥接无电沉积的金属与织物元件和衬底的改善的带负电的聚电解质层。值得注意地，电导性金属对织物衬底的粘附可以通过带负电的聚电解质PMANa或PAANa层的这种表面改性来大大改善，其中这些电导性织物的电性能可以在重复的摩擦、拉伸和洗涤循环下更可靠、坚固和耐久。此外，可以在环境和水性条件下不使用任何强化学品来进行用于制备带负电的聚电解质的原位自由基聚合方法。
本领域技术人员应了解，除非特别描述，否则在不偏离本发明的范畴的情况下，本文所述的本发明易于进行变化和修改。应该认为本领域的技术人员显而易见的所有这些变化和修改属于上文广泛描述的本发明的精神和范畴内。应理解，本发明包括所有这些变化和修改。本发明还包括说明书中个别或总体提及或指示的所有步骤和特征，以及所述步骤或特征的任何两个或超过两个的任何和所有组合。
在本说明书中对任何现有技术的参考并非并且不应视为承认或任何形式地建议现有技术形成常用常识的一部分。
Claims (7)
1.一种生产电导性织物元件的方法，其包括如下步骤：
(i)将所述织物元件的表面硅烷化以提供硅烷化表面；
(ii)通过原位自由基聚合将带负电的聚电解质接枝到所述硅烷化表面；
(iii)通过离子交换向聚电解质添加金属离子；
(iv)将金属离子还原为元素金属；和
(v)用金属粒子涂布所述织物元件，其中所述带负电的聚电解质包括聚(甲基丙烯酸钠盐)和聚(丙烯酸钠盐)中的至少一种。
2.如权利要求1所述的方法，其中步骤(v)包括用金属粒子通过无电金属沉积涂布所述织物元件。
3.如权利要求1或2所述的方法，其中所述金属粒子包括铜和镍粒子中的至少一种。
4.如权利要求1或2所述的方法，其中所述织物元件包括被配置来形成织品的纱线和纤维中的至少一种。
5.如权利要求1或2所述的方法，其中所述织物元件包括聚酯、尼龙、棉和丝线或纤维中的至少一种。
6.一种电导性织物元件，其通过根据权利要求1至5中任一项所述的方法步骤生产。
7.一种由至少一个织物元件形成的织品，其中所述至少一个织物元件通过根据权利要求1至5中任一项所述的方法步骤生产。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HK15102150 | 2015-03-03 | ||
| HK15102150.5 | 2015-03-03 | ||
| PCT/IB2016/000132 WO2016139521A1 (en) | 2015-03-03 | 2016-02-16 | An electrically conductive textile element and method of producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107614783A CN107614783A (zh) | 2018-01-19 |
| CN107614783B true CN107614783B (zh) | 2020-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201680013354.7A Active CN107614783B (zh) | 2015-03-03 | 2016-02-16 | 电导性织物元件及其制备方法 |
Country Status (9)
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| US (2) | US20180080171A1 (zh) |
| EP (1) | EP3265605B1 (zh) |
| JP (1) | JP6736573B2 (zh) |
| CN (1) | CN107614783B (zh) |
| ES (1) | ES2884301T3 (zh) |
| HK (2) | HK1220860A2 (zh) |
| HU (1) | HUE055483T2 (zh) |
| PL (1) | PL3265605T3 (zh) |
| WO (1) | WO2016139521A1 (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6786609B2 (ja) | 2016-07-27 | 2020-11-18 | エプロ ディベロップメント リミテッド | シリコンナノ粒子の製造及びその使用における改良 |
| KR101863276B1 (ko) * | 2017-01-12 | 2018-05-31 | 한국과학기술연구원 | 용해 공정을 이용한 복합 재료 리페어 방법 및 장치 |
| TWI671453B (zh) | 2018-09-14 | 2019-09-11 | 安炬科技股份有限公司 | 石墨烯導電織物之製造方法 |
| KR102620871B1 (ko) | 2020-12-10 | 2024-01-04 | 인하대학교 산학협력단 | 번역 기반 문장 데이터 변형과 딥러닝 보정을 이용한 문장 분류 데이터 증강 방법 및 장치 |
| CN114277474A (zh) * | 2021-12-23 | 2022-04-05 | 江南大学 | 一种纱线表面镀层的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3801478A (en) * | 1972-01-27 | 1974-04-02 | Cottbus Textilkombinat | Process of metallizing polymeric materials |
| CN102165114A (zh) * | 2008-07-15 | 2011-08-24 | 海克原料股份公司 | 固体表面上的多功能响应型功能层及其制备方法 |
| CN102995395A (zh) * | 2011-09-15 | 2013-03-27 | 香港理工大学 | 一种导电纺织品及其制作方法 |
| KR20140120672A (ko) * | 2013-04-04 | 2014-10-14 | 제일모직주식회사 | 전자파 차폐특성이 우수한 탄소나노섬유 복합체의 제조방법 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA990679A (en) * | 1971-11-22 | 1976-06-08 | Veb Textilkombinat Cottbus | Electroplating organic polymer film carrying grafted metal salt |
| DE3301669A1 (de) * | 1983-01-20 | 1984-07-26 | Bayer Ag, 5090 Leverkusen | Blitzschutzverbundmaterial |
| JPH04160164A (ja) * | 1990-01-08 | 1992-06-03 | Mitsui Petrochem Ind Ltd | 金属メッキされたα−オレフィン系重合体不織布およびその製造方法、ならびに該不織布からなる電磁波シールド材 |
| US7468332B2 (en) * | 2005-09-02 | 2008-12-23 | Jamshid Avloni | Electroconductive woven and non-woven fabric |
| WO2008133672A2 (en) * | 2006-12-22 | 2008-11-06 | Drexel University | Nanowires and coatings of self-assembled nanoparticles |
| CN102121194B (zh) * | 2010-01-11 | 2013-08-14 | 香港理工大学 | 导电织物制造方法及其制造的织物 |
| GB201303284D0 (en) * | 2013-02-25 | 2013-04-10 | Sec Dep For Business Innovation And Skills The | Conductive fabric |
| JP2016160480A (ja) * | 2015-02-28 | 2016-09-05 | 住江織物株式会社 | めっき繊維及びその製造方法 |
-
2016
- 2016-02-16 US US15/554,695 patent/US20180080171A1/en not_active Abandoned
- 2016-02-16 PL PL16758509T patent/PL3265605T3/pl unknown
- 2016-02-16 EP EP16758509.0A patent/EP3265605B1/en active Active
- 2016-02-16 WO PCT/IB2016/000132 patent/WO2016139521A1/en active Application Filing
- 2016-02-16 CN CN201680013354.7A patent/CN107614783B/zh active Active
- 2016-02-16 HU HUE16758509A patent/HUE055483T2/hu unknown
- 2016-02-16 JP JP2017546736A patent/JP6736573B2/ja active Active
- 2016-02-16 ES ES16758509T patent/ES2884301T3/es active Active
- 2016-03-01 HK HK16102377.1A patent/HK1220860A2/zh not_active IP Right Cessation
-
2018
- 2018-06-28 HK HK18108319.7A patent/HK1248780A1/zh unknown
-
2019
- 2019-10-04 US US16/593,885 patent/US20200071877A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3801478A (en) * | 1972-01-27 | 1974-04-02 | Cottbus Textilkombinat | Process of metallizing polymeric materials |
| CN102165114A (zh) * | 2008-07-15 | 2011-08-24 | 海克原料股份公司 | 固体表面上的多功能响应型功能层及其制备方法 |
| CN102995395A (zh) * | 2011-09-15 | 2013-03-27 | 香港理工大学 | 一种导电纺织品及其制作方法 |
| KR20140120672A (ko) * | 2013-04-04 | 2014-10-14 | 제일모직주식회사 | 전자파 차폐특성이 우수한 탄소나노섬유 복합체의 제조방법 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3265605B1 (en) | 2021-06-02 |
| HUE055483T2 (hu) | 2021-11-29 |
| PL3265605T3 (pl) | 2022-01-31 |
| ES2884301T3 (es) | 2021-12-10 |
| JP6736573B2 (ja) | 2020-08-05 |
| EP3265605A4 (en) | 2018-10-24 |
| HK1220860A2 (zh) | 2017-05-12 |
| EP3265605A1 (en) | 2018-01-10 |
| US20180080171A1 (en) | 2018-03-22 |
| CN107614783A (zh) | 2018-01-19 |
| HK1248780A1 (zh) | 2018-10-19 |
| JP2018512514A (ja) | 2018-05-17 |
| US20200071877A1 (en) | 2020-03-05 |
| WO2016139521A1 (en) | 2016-09-09 |
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