CN116409036A - 一种可重复使用纳米纤维层压复合医用防护服面料及其制备方法 - Google Patents

一种可重复使用纳米纤维层压复合医用防护服面料及其制备方法 Download PDF

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CN116409036A
CN116409036A CN202310339343.XA CN202310339343A CN116409036A CN 116409036 A CN116409036 A CN 116409036A CN 202310339343 A CN202310339343 A CN 202310339343A CN 116409036 A CN116409036 A CN 116409036A
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nanofiber
fabric
laminated composite
reusable
medical protective
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刘雍
高涵超
付中平
魏梦辰
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Hebei Textile Research Institute
Tianjin Polytechnic University
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Hebei Textile Research Institute
Tianjin Polytechnic University
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Abstract

本发明提供了一种可重复使用纳米纤维层压复合医用防护服面料及其制备方法。所述的可重复使用纳米纤维层压复合医用防护服面料由含导电纤维的机织外层面料、静电纺褶皱结构超疏水纳米纤维膜、具有单向导湿功能的机织内层面料构成，各层面料间通过热熔胶网膜黏合和层压技术复合而成。所制得的纳米纤维层压复合面料，消毒灭菌前耐静水压为30‑55kPa，抗合成血液穿透等级为3‑4级，透湿率为5000‑7000g/m2/d，对面料进行20次压力蒸汽灭菌后，耐静水压仍可达20‑40kPa，抗合成血液穿透等级3‑4级，透湿率4000‑7000g/m2/d。

Description

一种可重复使用纳米纤维层压复合医用防护服面料及其制备 方法
技术领域
本发明涉及医用防护材料技术领域，尤其是涉及一种可重复使用纳米纤维层压复合医用防护服面料及其制备方法。
背景技术
过去三年多来，医用防护服等防护物资使用量大，医疗防护服废弃物总量骤增，一次性防护服“用即弃”特性带来大量的医疗废物处理问题。目前多采用高温焚烧方式处理废弃防护服，易造成大气污染，同时在废弃处理中存在工人感染风险。提高医用防护服使用频次，开发可重复使用医用防护服可以从源头上减轻医疗废弃物对环境的污染，有效缓解防护物资废弃处理问题，达到节约资源、保护环境的效果，因此亟需开发兼具高防护性和可重复使用性的新型医用防护服面料。
医用防护服面料首先需具备优异的防护性能，能够有效阻隔外界液态水、血液、气溶胶穿透，在传染性环境中降低人员感染风险，医用防护服面料还需具备优异的物理机械性能和舒适性，具有良好的透气透湿性，提高医护人员的穿着舒适度。目前市面上的防护服材料如3M公司生产的纺粘基布聚乙烯覆膜材料，其透湿率仅为40g/m2/d，而理想医用防护服面料的透湿率应不低于2500g/m2/d，因此穿着过程中身体产生的湿气和热量不能及时排出，影响医护人员的身体健康和工作效率。静电纺纳米纤维膜具有纤维直径细、孔径小、孔隙率高的优点，能同时具备优异的阻隔防护性和透气透湿性，成为最具前景的医用防护服材料。
可重复使用医用防护服是指使用后经过必要洗涤消毒处理后依然能够提供有效防护性能的医用防护服，相比医用一次性防护服，可重复使用防护服能有效解决防护服供需短缺问题，减轻医疗废弃物对环境的污染，但同时对材料的物理机械性能、耐用性提出了更高的要求。目前医疗行业消毒灭菌方法主要包括压力蒸汽灭菌、环氧乙烷气体灭菌、辐照灭菌、含氯消毒剂灭菌、75％乙醇灭菌。现有专利技术通过在纳米纤维膜上浸渍氟碳整理剂，提高纳米纤维膜的拒水拒血液性能，但多次洗消处理会降低整理剂拒水效果，导致纳米纤维膜防护性能下降，无法满足可重复使用要求。此外，单层纳米纤维膜物理机械性能差，经过多次洗消处理后无法保证其尺寸稳定性和面料完整性。
专利CN111575904B“具有褶皱结构的超弹防水透气皮肤敷料及其制备方法”，通过调控两层静电纺纤维膜中交联密度差异，使上下层纤维膜的热收缩率产生差异，在外界温度作用下得到褶皱结构超弹防水透气皮肤敷料，皮肤敷料的耐静水压为5-50KPa，上述专利与本发明的材料与制备方法有本质区别，且该方法需要先制备上下双层膜结构，纤维膜热收缩率难以精确调控。
专利CN115672053A“一种具有褶皱结构的超疏水纤维膜及制备”，通过共价接枝的方式在在聚丙烯纤维膜表面生长出类褶皱形貌微纳结构，该专利仅公布了纤维膜的水接触角为151-154°，油水分离中对水的截留率可达99％以上，该专利并未考察纤维膜的耐静水压值。
专利CN111501325B“一种表面褶皱化纤维类材料及其制备方法”，在材料基体上形成由树脂和稀释剂组成的树脂涂布液涂层，使用等离子体处理使涂层原位交联，在在纤维轴形成环状排列褶皱。上述专利与本发明的材料与制备方法有本质区别，该专利仅公布了织物的水接触角大于150°，并未考察其耐静水压性能。
专利CN114804648A“一种无氟自清洁涂层及其制备方法和应用”，利用石墨烯的褶皱结构，结合纳米二氧化硅，构建微纳结构，制备得到超疏水自清洁涂层。上述专利与本发明的材料与制备方法有本质区别，专利仅公布了纤维膜的水接触角为150-165°，并未考察纤维膜的耐静水压值。
发明内容
本发明的目的在于解决现有静电纺纳米纤维膜经过多次洗涤消毒处理后防护性能下降，可重复使用性差问题，提供一种可重复使用纳米纤维层压复合医用防护服面料及其制备方法。
本发明采用溶剂-热诱导法在静电纺纳米纤维表面构筑稳定的褶皱结构。在溶剂和加热共同作用下纳米纤维发生溶胀，纳米纤维表面和内部会产生差异性热胀行为，当纤维表面和内部界面处的应变大于起皱应变时，为保持体系能量最低，纳米纤维表面形成褶皱结构，然后使用疏水剂对具有褶皱结构的纳米纤维膜进行浸渍后整理。褶皱结构的引入，大大提高了纳米纤维膜的疏水性，使其在消杀处理后，仍然能有效阻隔外界液态水和血液穿透。采用热熔胶网膜黏合和层压技术将疏水纳米纤维层与含抗静电纤维的机织外层面料、单向导湿机织内层面料复合，制得具有三明治结构的纳米纤维层压复合面料，经过多次消毒灭菌处理后，纳米纤维层压复合面料依然具有优异的疏水性和力学性能，能有效阻隔外界液态水和血液渗透，同时兼具良好的透湿性，多次消杀后面料能够可重复使用。
为达到上述目的，本发明采用的技术方案如下：
一种可重复使用纳米纤维层压复合医用防护服面料，由含导电纤维的机织外层面料、静电纺褶皱结构超疏水纳米纤维膜、具有单向导湿功能的机织内层面料构成，各层面料间通过热熔胶网膜黏合和层压技术复合，制成具有三明治结构的纳米纤维层压复合面料。
所述褶皱结构超疏水纳米纤维膜按照如下步骤的方法制备：
(1)将聚合物溶解到溶剂中，充分搅拌得到纺丝溶液，通过静电纺丝技术制备纳米纤维膜；
(2)将纳米纤维膜放入高压水热反应釜中，向反应釜中加入盐酸、去离子水和少量醇类溶剂，将纳米纤维膜浸没到溶液中，高温反应一段时间后将纳米纤维膜取出，使用去离子水对纳米纤维膜进行反复冲洗；
(3)使用疏水剂对纳米纤维膜进行浸渍整理，然后将纳米纤维膜烘干；
所述步骤(1)中所述聚合物为聚偏二氟乙烯、聚酰亚胺、聚醚酰亚胺、聚醚砜或聚砜；所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、环己烷、二氯甲烷、氯仿中的一种或以上；所述纺丝溶液中聚合物浓度为10-30wt％。
所述步骤(1)中静电纺丝工艺参数：纺丝电压10-30kV，溶液灌注速度0.5-5ml/h，接收距离5-30cm，环境温度10-30℃，相对湿度20-60％。
所述步骤(2)中盐酸的浓度为36-38％；所述醇类溶剂为乙醇、正丁醇、丙二醇、或异丙醇，醇类溶剂占高压反应釜中去离子水的质量分数为3％-10％；步骤(2)中反应温度为120-160℃，反应时间为4-8小时；将纳米纤维膜取出后使用去离子水冲洗3-5次。
如上所述的制备方法，所述疏水剂为含氟丙烯酸酯、无氟丙烯酸、聚二甲基硅氧烷或聚二甲基羟基硅氧烷。
所述褶皱结构超疏水纳米纤维膜的克重为20-60g/m2，纤维直径为100-1000nm，平均孔径为0.5-2.0μm，孔隙率为50-90％，水接触角为150-160°，耐静水压为10-50KPa，抗合成血液穿透等级为3-4级，透湿率为5000-7000g/m2/d。
在所述褶皱结构超疏水纳米纤维膜的基础上，本发明提供了一种可重复使用纳米纤维层压复合医用防护服面料，由外层含导电纤维的机织面料、中间层褶皱结构超疏水纳米纤维膜内层单向导湿机织面料通过热熔胶网膜黏合和层压技术复合而成。
所述可重复使用纳米纤维层压复合医用防护服面料，按照下述方法制备：
(1)在外层机织面料与中间层纳米纤维膜间、中间层纳米纤维膜与内层机织面料间放置热熔胶网膜；
(2)将外层机织面料、中间层纳米纤维膜、内层机织面料与热熔胶网膜共同放置在热压机的放布区域，通过层压工艺对面料进行复合。
如上所述的制备方法，热熔胶网膜为聚酰胺、聚醚砜、热塑性聚氨酯或乙烯-醋酸乙烯酯共聚物。
如上所述的制备方法，层压工艺参数：热压温度80-150℃，压力0.5-3MPa，热压时间1-5分钟。
如上所述的制备方法，外层机织面料由棉纤维、涤纶纤维、粘胶纤维等纤维单独或混合后与导电纤维混纺织制的机织物面料，其中导电纤维可为金属导电纤维、碳素导电纤维或有机聚合物导电纤维。
如上所述的制备方法，内层单向导湿机织面料由异型截面涤纶纤维、中空多孔涤纶纤维、细旦涤纶或细旦丙纶纤维制成。
本发明制备的可重复使用纳米纤维层压复合医用防护服面料，消毒灭菌前面料的耐静水压为30-55kPa，抗合成血液穿透等级为3-4级，透湿率为5000-7000g/m2/d，对纳米纤维层压复合医用防护服面料进行20次压力蒸汽灭菌(温度121℃、压力102.9kPa)后，面料的耐静水压仍可达20-40kPa，抗合成血液穿透等级3-4级，透湿率4000-7000g/m2/d。
有益效果：
本发明制备的一种可重复使用纳米纤维层压复合医用防护服面料，由褶皱结构超疏水纳米纤维膜与外层含抗静电纤维的机织面料、内层单向导湿机织面料层压复合而成；纳米纤维表面褶皱结构可增加纤维表面粗糙度，大大提高纳米纤维膜疏水性，有效阻止外界液态水和血液渗透，经过多次消毒灭菌后依然具有良好的防护性能；外层含导电纤维的机织面料，可有效避免静电积聚，同时提供足够的断裂强力、撕破强力、耐磨损性和抗穿刺性；内层单向导湿机织面料具有良好的透气透湿性，能够提升面料的穿着舒适性。
本发明制备的一种可重复使用纳米纤维层压复合医用防护服面料，集高防护、高透湿、可重复使用性能于一体，可经受20次以上消毒灭菌流程，织物外观不发生明显变化，且耐静水压、抗合成血液穿透、透湿率指标仍可满足GB19082-2009《医用一次性防护服技术要求》。
附图说明
图1为本发明可重复使用纳米纤维层压复合医用防护服面料。
其中：1-含导电纤维的机织外层面料；2-静电纺褶皱结构超疏水纳米纤维膜；3-具有单向导湿功能的机织内层面料。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例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做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。
实施例中的热熔胶网膜厂家均为上海星霞高分子制品有限公司，实施例1中聚酰胺热熔胶网膜商品牌号为XWA116，实施例2和3中热塑性聚氨酯热熔胶网膜商品牌号为HWU98。
实施例1
参照图1所示，本实施例公开了一种可重复使用纳米纤维层压复合医用防护服面料，由含导电纤维的机织外层面料1、静电纺褶皱结构超疏水纳米纤维膜2、具有单向导湿功能的机织内层面料3构成，各层面料间通过热熔胶网膜黏合和层压技术复合，制成具有三明治结构的纳米纤维层压复合面料。
而可重复使用纳米纤维层压复合医用防护服面料的制备方法，步骤如下：
(1)将聚醚酰亚胺溶解在N-甲基吡咯烷酮中，磁力搅拌8h得到质量浓度为20wt％的纺丝溶液；将纺丝溶液置于供液装置内，接通高压电源，静电纺丝工艺参数为：纺丝电压25kV，接收距离20cm，溶液灌注速度0.8mL/h，环境温度20℃，相对湿度40％；
(2)向高压水热反应釜中加入36％浓度的盐酸、去离子水和正丁醇，盐酸与去离子水质量比为1:1，正丁醇占去离子水的质量分数为3％，将聚醚酰亚胺浸入溶液中，在140℃下反应4小时，将纳米纤维膜取出后使用去离子水冲洗3次；
(3)将聚醚酰亚胺纳米纤维膜在含氟丙烯酸酯乳液中浸泡0.5h，乳液中含氟丙烯酸酯质量浓度为2wt％，然后将纳米纤维膜取出并烘干，烘干温度为60℃，时间为2小时；
其中所用的含氟丙烯酸酯乳液为购自3M公司的产品Novec-1700；
(4)在聚醚酰亚胺纳米纤维膜、涤纶长丝/镀银纤维混纺制成的平纹组织结构机织外层、细旦丙纶制成的平纹组织结构机织内层之间放置聚酰胺热熔胶网膜并进行层压复合，热压温度135℃，压力0.5MPa，热压时间1min。
最终制得的可重复使用纳米纤维层压复合医用防护服面料，耐静水压为40kPa，抗合成血液穿透等级为4级，透湿率为5200g/m2/d，对纳米纤维层压复合医用防护服面料进行10次压力蒸汽灭菌(温度121℃、压力102.9kPa)后，面料的耐静水压仍可达30kPa，抗合成血液穿透等级4级，透湿率5000g/m2/d。
对比例1
可重复使用纳米纤维层压复合医用防护服面料的制备方法，基本同实施例1，不同之处仅在于没有经过步骤(2)，制得的纳米纤维膜表面不具有褶皱结构，最终制得的纳米纤维层压复合面料耐静水压为35kPa，抗合成血液穿透等级为4级，透湿率为4900g/m2/d，对纳米纤维层压复合医用防护服面料进行10次压力蒸汽灭菌(温度121℃、压力102.9kPa)后，面料的耐静水压为15kPa，抗合成血液穿透等级4级，透湿率4800g/m2/d；将对比例1与实施例1进行比较可以看出经10次压力蒸汽灭菌后面料的耐静水压明显不如实施例1，这是因为对比例1中纳米纤维膜表面不具有褶皱结构，仅依靠疏水剂浸渍后整理使纳米纤维膜具有疏水性，但疏水剂的拒水性在10次压力蒸汽灭菌后减弱，导致面料的耐静水压在多次消毒灭菌后明显下降。
实施例2
可重复使用纳米纤维层压复合医用防护服面料的制备方法，步骤如下：
(1)将聚偏二氟乙烯溶解在N,N-二甲基甲酰胺中，在60℃下磁力搅拌8h得到质量浓度为18wt％的纺丝溶液；将纺丝溶液置于供液装置内，接通高压电源，静电纺丝工艺参数为：纺丝电压20kV，接收距离20cm，溶液灌注速度1mL/h，环境温度20℃，相对湿度40％；
(2)向高压水热反应釜中加入盐酸、去离子水和正丁醇，盐酸与去离子水质量比为1:1，正丁醇占去离子水的质量分数为4％，将聚偏二氟乙烯浸入溶液中，在150℃下反应4小时，将纳米纤维膜取出后使用去离子水冲洗3次；
(3)将聚偏二氟乙烯纳米纤维膜在聚二甲基硅氧烷中浸泡0.5h，然后将纳米纤维膜取出并烘干；
(4)在聚偏二氟乙烯纳米纤维膜、棉纤维/涤纶长丝/镀银纤维混纺制成的平纹组织结构机织外层、异性截面涤纶纤维制成的平纹组织结构机织内层之间放置热塑性聚氨酯热熔胶网膜并进行层压复合，热压温度140℃，压力1MPa，热压时间1min。
最终制得的可重复使用纳米纤维层压复合医用防护服面料，耐静水压为38kPa，抗合成血液穿透等级为4级，透湿率为5500g/m2/d，对纳米纤维层压复合医用防护服面料进行20次压力蒸汽灭菌(温度121℃、压力102.9kPa)后，面料的耐静水压仍可达27kPa，抗合成血液穿透等级4级，透湿率5300g/m2/d。
实施例3
可重复使用纳米纤维层压复合医用防护服面料的制备方法，步骤如下：
(1)将聚醚砜溶解在N,N-二甲基乙酰胺中，磁力搅拌8h得到质量浓度为18wt％的纺丝溶液；将纺丝溶液置于供液装置内，接通高压电源，静电纺丝工艺参数为：纺丝电压25kV，接收距离20cm，溶液灌注速度1mL/h，环境温度20℃，相对湿度40％；
(2)向高压水热反应釜中加入盐酸、去离子水和乙醇，盐酸与去离子水质量比为1:1，乙醇占去离子水的质量分数为5％，将聚醚砜浸入溶液中，在150℃下反应4小时，将纳米纤维膜取出后使用去离子水冲洗3次；
(3)将聚醚砜纳米纤维膜在聚二甲基羟基硅氧烷中浸泡0.5h，然后将纳米纤维膜取出并烘干；
(4)在聚醚砜纳米纤维膜、棉纤维/镀银纤维混纺制成的斜纹组织结构机织外层、中空多孔涤纶纤维制成的斜纹组织结构机织内层之间放置热塑性聚氨酯热熔胶网膜并进行层压复合，热压温度100℃，压力1MPa，热压时间0.5min。
最终制得的可重复使用纳米纤维层压复合医用防护服面料，耐静水压为45kPa，抗合成血液穿透等级为4级，透湿率为6200g/m2/d，对纳米纤维层压复合医用防护服面料进行15次压力蒸汽灭菌(温度121℃、压力102.9kPa)后，面料的耐静水压仍可达30kPa，抗合成血液穿透等级4级，透湿率5900g/m2/d。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (6)

1.一种可重复使用的纳米纤维层压复合医用防护服面料，其特征在于，外层为含导电纤维的机织面料、中间层为静电纺褶皱结构超疏水纳米纤维膜、内层为具有单向导湿功能的机织面料，各层面料间通过热熔胶网膜黏合和层压技术复合而成；消毒灭菌前面料的耐静水压为30-55kPa，抗合成血液穿透等级为3-4级，透湿率为5000-7000g/m2/d，对纳米纤维层压复合医用防护服面料在120℃、102.9kPa条件下进行20次压力蒸汽灭菌后，面料的耐静水压仍可达20-40kPa，抗合成血液穿透等级3-4级，透湿率4000-7000g/m2/d。
2.根据权利要求1所述的可重复使用的纳米纤维层压复合医用防护服面料，其特征在于，所述褶皱结构超疏水纳米纤维膜按照如下步骤制备：
(1)将聚合物溶解到溶剂中，充分搅拌得到纺丝溶液，通过静电纺丝技术制备纳米纤维膜；
(2)将纳米纤维膜放入高压水热反应釜中，向反应釜中加入盐酸、去离子水和少量醇类溶剂，将纳米纤维膜浸没到溶液中，高温反应一段时间后将纳米纤维膜取出，使用去离子水对纳米纤维膜进行反复冲洗；
(3)使用疏水剂对纳米纤维膜进行浸渍整理，然后将纳米纤维膜烘干；
其中，步骤(2)中所述醇类溶剂为乙醇、正丁醇、丙二醇或异丙醇中的一种或多种，醇类溶剂占高压反应釜中去离子水质量分数的3％-10％，反应温度为120-160℃，反应时间为4-8小时。
3.根据权利要求2所述的可重复使用的纳米纤维层压复合医用防护服面料，其特征在于，步骤(3)中所述疏水剂为含氟丙烯酸酯、无氟丙烯酸、聚二甲基硅氧烷或聚二甲基羟基硅氧烷中的一种或多种。
4.一种权利要求1所述可重复使用的纳米纤维层压复合医用防护服面料的制备方法，其特征在于，包括如下步骤：
(1)在外层机织面料与中间层纳米纤维膜间、中间层纳米纤维膜与内层机织面料间放置热熔胶网膜；
(2)将外层机织面料、中间层纳米纤维膜、内层机织面料与热熔胶网膜共同放置在热压机的放布区域，通过层压工艺对面料进行复合；
其中，所述步骤(1)中的热熔胶网膜为聚酰胺、聚醚砜、热塑性聚氨酯或乙烯-醋酸乙烯酯共聚物中的一种或多种。
5.根据权利要求4所述可重复使用的纳米纤维层压复合医用防护服面料的制备方法，其特征在于，所述步骤(2)中层压工艺参数为：热压温度80-150℃，压力0.5-3MPa，热压时间1-5min。
6.根据权利要求4所述可重复使用的纳米纤维层压复合医用防护服面料的制备方法，其特征在于，所述外层机织面料由棉纤维、涤纶纤维、粘胶纤维等纤维单独或混合后与导电纤维混纺织制的机织物面料，其中导电纤维可为金属导电纤维、碳素导电纤维或有机聚合物导电纤维；所述内层单向导湿机织面料由异型截面涤纶纤维、中空多孔涤纶纤维、细旦涤纶或细旦丙纶纤维制成。
CN202310339343.XA 2023-03-31 2023-03-31 一种可重复使用纳米纤维层压复合医用防护服面料及其制备方法 Pending CN116409036A (zh)

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