CN115302866A - 一种抗菌防紫外线高效低阻微纳米纤维口罩面料及其制备方法 - Google Patents

一种抗菌防紫外线高效低阻微纳米纤维口罩面料及其制备方法 Download PDF

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CN115302866A
CN115302866A CN202210928277.5A CN202210928277A CN115302866A CN 115302866 A CN115302866 A CN 115302866A CN 202210928277 A CN202210928277 A CN 202210928277A CN 115302866 A CN115302866 A CN 115302866A
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nanofiber
nano
ultraviolet
efficiency low
antibacterial agent
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贾琳
王西贤
边立然
董晓
汤小龙
衡冲
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Henan Institute of Engineering
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Henan Institute of Engineering
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    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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Abstract

本发明属于纺织领域，提供一种抗菌防紫外线高效低阻微纳米纤维口罩面料及其制备方法。所述抗菌防紫外线高效低阻微纳米纤维口罩面料为三明治结构，包括内层、中间层和外层；所述内层为亲水层，中间层为含有光催化复合抗菌剂的纳米纤维膜，外层为疏水层。所述光催化复合抗菌剂为纳米级的Ag、GO或非金属离子掺杂的光催化抗菌剂。本发明通过静电纺丝制得PP纺粘无纺布‑纳米纤维膜分别作为外层和中间层，再覆盖黏胶水刺无纺布作为内层，即得口罩面料产品。本发明的口罩面料具有高效低阻的过滤性能及良好的抑菌性能和防紫外线性能，同时还具有纳米纤维较高的比表面积和较大的孔隙率，结构独特，性能优异；生产过程一次成型，节约成本和能源。

Description

一种抗菌防紫外线高效低阻微纳米纤维口罩面料及其制备 方法
技术领域
本发明属于纺织领域，涉及纺织面料材料的制备，尤其涉及一种抗菌防紫外线高效低阻微纳米纤维口罩面料及其制备方法。
背景技术
近年来，由于空气污染的加剧以及新冠疫情的全球性发生，佩戴口罩已成为人们日常生活的标配。口罩属于纤维类纺织品，目前常用的口罩面料主要是由熔喷驻极无纺布、纺粘无纺布和纤维过滤材料组成的三层结构，其中多数的纤维类过滤材料由于纤维直径和孔隙尺寸较大，对PM2.5以下的微小颗粒物和病毒的阻隔过滤能力较差；而人们在佩戴口罩时由于不断呼吸会导致口罩内部滋生大量的细菌，因此口罩面料还需要较高的抑菌能力，否则长久佩戴也会影响人们的身体健康；再加上人们审美意识的不断提高，在夏季格外注重皮肤防晒，如果口罩在阻隔污染物和病毒的同时还能够隔离紫外线，将更加符合人们的使用需求。因此高效低阻、抗菌性好且具备防紫外线能力的口罩类面料具有更广的市场应用价值。
纳米级的光催化抗菌剂（如TiO2、ZnO、MgO等）是一类氧化物半导体材料，具有优异的电学性质、光学性质和化学稳定性，其价带上的电子可以吸收紫外线中的能量发生跃迁，使其具备吸收屏蔽紫外线和光催化抗菌的能力：首先，由于纳米级的光催化抗菌剂（如TiO2、ZnO、MgO等）粒径小于紫外线的波长，当紫外线照射时，光催化抗菌剂（如TiO2、ZnO、MgO等）的粒子可以将作用在其表面的紫外线向各个方向散射，从而减小紫外线的照射强度；同时，光催化抗菌剂对细菌具有选择毒性，对革兰氏阳性菌和革兰氏阴性菌都具有较好的抗菌活性，对人体正常的细胞影响较小，具有安全、高效、光谱抗菌、生物相容性及不产生耐药性的特点。例如，贾琳等人采用静电纺丝技术，以SiO2作为驻极体制备的PAN/SiO2复合驻极纳米纤维膜，与纯PAN（聚丙烯腈）纳米纤维滤膜相比，具有更高的透气率、过滤效率和更低的阻力压降，过滤性能更优，有望开发高效低阻的空气过滤材料。[贾琳, 王西贤, 曹琪龙,等. PAN/SiO2复合纳米纤维滤膜的制备及性能分析[J]. 丝绸, 2020, 57(10):7]但是，纳米级的光催化抗菌剂（如TiO2、ZnO、MgO等）的禁带宽度仅为 3.0-3.2eV，对可见光的利用率极低，只能通过吸收波长375nm以下的紫外光发挥抗菌作用，而这部分光源仅占太阳光能的4%，这极大限制了纳米级的光催化抗菌剂在抗菌领域的应用和发展。因此，将纳米级的光催化抗菌剂应用于口罩面料的制备，在有效利用纳米级的光催化抗菌剂的优点同时规避其缺点，对于提高口罩面料的抗菌性能和防紫外线能力具有重要意义。
发明内容
针对传统口罩面料抗菌性能和防紫外线能力有限的技术问题，本发明提出一种抗菌防紫外线高效低阻微纳米纤维口罩面料及其制备方法，所制备的口罩面料既具有普通口罩的防雾霾、防颗粒物污染、阻隔飞沫、抗病毒等基本功能，又具有优异的过滤性能，即高过滤效率和低阻力压降，同时还兼具优异的抗菌性、防紫外线、亲肤舒适和防水透气等多重功能。
为了达到上述目的，本发明采用以下技术方案：
一种抗菌防紫外线高效低阻微纳米纤维口罩面料，其结构是一种三明治结构，包括内层、中间层和外层；其中，所述内层为亲水的黏胶水刺无纺布，所述外层为疏水的PP纺粘无纺布，所述中间层为含有光催化复合抗菌剂的纳米纤维膜。
所述亲水的黏胶水刺无纺布具有洁净度高、亲水性好，舒适卫生的特点，在医疗卫材方面具有非常广泛的应用，能保证口罩面料与皮肤接触的内层具有优良的亲水性、透湿性，保证口罩的舒适性。
所述疏水的PP纺粘无纺布具有价格便宜、机械强度高、防水透气的特点，能保证口罩面料较高的机械性能，且保证口罩面料裸露在外的部分具有防水透气的功能。
所述纳米纤维膜的纤维直径＜500nm、孔隙率不低于90%、平均孔径＜4μm，面密度为0.5-10g/m2，同时纳米纤维膜具有纳米级的纤维直径和较高的孔隙率也使其具有较高的比表面积，因此该纳米纤维膜可有效阻隔PM2.5、PM0.3等细微颗粒物、细菌、病毒和花粉等，保证口罩面料具有高效低阻的功能。
优选的，所述纳米纤维膜内部的光催化复合抗菌剂均匀分布。所述光催化复合抗菌剂为纳米级的Ag、GO或非金属离子（S或N）掺杂的光催化抗菌剂（TiO2、ZnO或MgO），具有安全、高效、光谱抗菌和协同抗菌的效果，在可见光照射下，价带上的电子可以吸收可见光中的能量发生跃迁，可以吸收屏蔽紫外线，且通过生成的活性自由基对细菌的细胞膜、蛋白质和DNA等重要成分都造成损伤，从而导致细菌的死亡，对引起感染或病原性的革兰式阳性菌、革兰式阴性菌、真菌及病毒（如甲、乙肝和狂犬病毒等）等都具有广泛的杀灭及抑制作用，保证口罩面料具有优异的抗菌性和防紫外线双重功能。
本发明还进一步提供了抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：用有机溶剂溶解聚合物纳米纤维，得到质量分数为5-25%的聚合物纳米纤维溶液，向聚合物纳米纤维溶液中加入粒径为10-50nm的光催化复合抗菌剂，光催化复合抗菌剂的添加质量为聚合物纳米纤维溶液的质量的0.5-2%，先利用超声波将光催化复合抗菌剂在纳米纤维溶液中超声20min-2h，然后在室温下搅拌8-24h,使溶液均匀澄清，然后使溶液静置到消泡，得到含有光催化复合抗菌剂的聚合物纳米纤维溶液，作为纺丝液。
（2）制备PP无纺布-纳米纤维膜：将步骤（1）制得的纺丝液以一定的流速引入到无针头喷丝头处，利用无针头的规模化静电纺丝机制备纳米纤维膜；以面密度为15-50g/m2的PP纺粘无纺布作为接收基底，纺丝液流量为50-150mL/h，在无针头喷丝头处施加高压40-60kV；喷丝头沿垂直于PP纺粘无纺布运动的方向往复运动，保证纳米纤维均匀地喷覆在PP纺粘无纺布表面；PP纺粘无纺布以0.1m-1m/min的速度运动（取决于无针头喷丝头的个数），保证PP纺粘无纺布-纳米纤维膜制备的连续性，接收时间（即纺丝时间）为20min-1h，制得PP纺粘无纺布-纳米纤维膜，其中PP纺粘无纺布作为外层、纳米纤维膜作为中间层。
（3）制备抗菌防紫外线微纳米纤维口罩面料：将步骤（2）的PP纺粘无纺布-纳米纤维膜的纳米纤维膜表面再覆盖一层面密度为20-50g/m2的黏胶水刺无纺布作为口罩面料的内层，形成三明治结构，然后利用超声波粘合机剪切、粘合成新型的抗菌防紫外线高效低阻纳米纤维口罩，具有生产效率高，一次成型、节约成本和能源的特点。
优选的，所述步骤（1）中有机溶剂为二甲基甲酰胺（DMF）、三氟乙酸、二氯甲烷和三氯甲烷中的至少一种；所述聚合物纳米纤维为聚丙烯腈（PAN）纳米纤维、聚氨酯（PU）纳米纤维、聚酯（PET）纳米纤维、聚乳酸（PLLA）纳米纤维和聚己内酯（PCL）纳米纤维中的任一种。
优选的，所述步骤（1）的光催化复合抗菌剂中纳米Ag、纳米氧化石墨烯或纳米非金属离子与光催化抗菌剂的质量比为（0.05-1）：1。所述光催化复合抗菌剂具体为纳米Ag掺杂TiO2、纳米Ag掺杂ZnO、纳米Ag掺杂MgO、纳米GO掺杂TiO2、纳米GO掺杂ZnO、纳米GO掺杂MgO、纳米N掺杂TiO2、纳米N掺杂ZnO、纳米N掺杂MgO、纳米S掺杂TiO2、纳米S掺杂ZnO和纳米S掺杂MgO中的任一种。
本发明的有益效果：
（1）本发明直接将光催化复合抗菌剂加入到聚合物纳米纤维溶液中，利用超声波将光催化复合抗菌剂在聚合物纳米纤维溶液中超声，使光催化复合抗菌剂均匀地分散在聚合物溶剂中，再利用无针头的规模化静电纺丝机在PP纺粘无纺布表面直接喷覆具有高效低阻、抗菌及防紫外线多重功能的纳米纤维膜，将PP纺粘无纺布-纳米纤维膜表面再覆盖一层黏胶水刺无纺布作为口罩内层，形成三明治结构，利用超声波粘合机剪切、粘合成抗菌防紫外线高效低阻微纳米纤维口罩面料，生产效率高，节约成本和能源。
（2）本发明以纳米级的Ag、GO或非金属离子掺杂的光催化抗菌剂作为光催化复合抗菌剂，不仅发挥了光催化抗菌剂安全、高效、光谱抗菌、生物相容性、不产生耐药性以及减小紫外线照射强度的作用，而且经Ag、GO或非金属离子掺杂的光催化抗菌剂，可显著降低带隙能级，实现可见光的激发并抑制电子-空穴对的复合，在可见光照射下，光催化抗菌剂的光响应范围、电子空穴对数量都得到了大幅度提高，进而提高了光催化抗菌剂的抗菌性能和光催化效率。
（3）本发明制备的纳米纤维膜上均匀分布的光催化复合抗菌剂粒径为10-50nm，其较小的粒径可增强纳米纤维膜的静电吸附作用，具有协同抗菌的效果，附微细颗粒物、细菌和病毒等的效果更佳，在不增加阻力压降的情况下有效提高了纳米纤维膜的过滤效率。本发明制备的纳米纤维膜具有纳米级的纤维直径（＜500nm）、较高的孔隙率（90%以上）和较小的平均孔径（＜4μm），同时也具有较高的比表面积，可有效提高抗菌剂与PM2.5、PM0.3、花粉、细菌和病毒等接触的几率，大大地提高抗菌活性，同时也保证了对紫外线的吸收效率。
（4）本发明口罩面料的过滤效率为89-99.999%，阻力压降为20-115Pa，过滤效率优异，阻力压降低，且抑菌率为89.79-99.27%，紫外吸防护系数（UPF）为42-110，UVA的透射率为1.1-3.87%，实现了该口罩面料产品高效低阻的过滤性能以及良好的抑菌性能和防紫外线性能。
（5）本发明在制备过程中直接以充当口罩面料外层的PP纺粘无纺布作为接收基底进行纺丝，制备得到PP纺粘无纺布-纳米纤维膜，再进行内层覆盖，简化了口罩面料的制备流程，提高了生产效率，生产过程一次成型，节约成本和能源，附加值高；以疏水的PP纺粘无纺布作为外层具有价格便宜、机械强度高、防水透气的特点，能保证口罩面料较高的机械性能和防水透气的功能；以黏胶水刺无纺布作为内层具有较高的洁净度、亲水性和透湿性，与皮肤接触时不易产生刺激性。
附图说明
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。
图1为实施例1静电纺丝制备PP纺粘无纺布-纳米纤维膜示意图。
图2为实施例1的PP纺粘无纺布-纳米纤维膜成品图。
图3为实施例1的抗菌防紫外线高效低阻微纳米纤维口罩面料示意图。
图4为实施例1中PP纺粘无纺布的SEM图。
图5为实施例1 的抗菌防紫外线PAN/Ag-TiO2纳米纤维膜的SEM图。
图6为实施例1的抗菌防紫外线PAN/Ag-TiO2纳米纤维膜中Ag元素（a）和O元素（b）的扫描分布图。
图7为实施例1中纯PAN（a）和抗菌防紫外线PAN/Ag-TiO2纳米纤维膜（b）表面大肠杆菌菌落的培养情况图。
图8为实施例2的抗菌防紫外线PCL/Ag-ZnO纳米纤维膜的SEM图。
图9为实施例6的抗菌防紫外线PAN/GO-MgO纳米纤维膜的SEM图。
具体实施方式
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付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。
本发明的实施例中所使用的实验方法如无特殊说明，均为常规方法。
本发明的实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
一种抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：向质量分数为12%的PAN纳米纤维溶液（以DMF作为溶剂）中加入粒径为10-50nm的Ag掺杂TiO2光催化复合抗菌剂，Ag掺杂TiO2光催化复合抗菌剂的质量为PAN纳米纤维溶液的质量的1%，Ag掺杂TiO2光催化复合抗菌剂中Ag与TiO2的物质的量比为1:1；超声2h，使Ag掺杂TiO2光催化复合抗菌剂均匀地分散在PAN纳米纤维溶液中，然后在室温下搅拌24h，使溶液均匀澄清，再进行消泡，将得到的混合溶液作为纺丝液，备用。
（2）将步骤（1）制得的纺丝液用无针头的静电纺丝机进行静电纺丝。如图1所示，将面密度为20g/m2的PP纺粘无纺布卷绕在接收装置上，接收装置的运动速度为0.1m/min；将纺丝液放置于供液器中，将供液器与无针头喷丝头相连，供液器的流速设为100mL/h，保证纺丝液的供给；在检查电路无误后，打开面板上的高压发生器，将电压调到45kV，喷丝头沿垂直于PP纺粘无纺布的方向往复运动，保证纺丝液均匀地喷覆在PP纺粘无纺布的表面，纺丝40min，制备PP纺粘无纺布-纳米纤维膜，测得纳米纤维膜的面密度为1.2g/m2。
（3）将步骤（2）制得的PP纺粘无纺布-纳米纤维膜取下，在纳米纤维膜面覆盖上一层25g/m2的黏胶水刺无纺布，利用超声波粘合机进行剪切和粘合，制得抗菌防紫外线高效低阻微纳米纤维口罩面料。
图2为PP纺粘无纺布-纳米纤维膜成品图，图中有一角折起的面料层为PP纺粘无纺布，下部平铺的面料层为纳米纤维膜。
图3为抗菌防紫外线高效低阻微纳米纤维口罩面料示意图，口罩面料由内到外依次为黏胶水刺无纺布、纳米纤维膜和PP纺粘无纺布。
图4为PP纺粘无纺布的SEM图，从图中可知，PP纺粘无纺布的纤维较粗，直径为27μm。
图5为本实施例的抗菌防紫外线PAN/Ag-TiO2纳米纤维的SEM图，由图可知，该纳米纤维的直径比较均匀，大多数Ag和TiO2纳米颗粒均匀地分布在PAN纳米纤维的内部，个别PAN纳米纤维的表面有Ag和TiO2纳米颗粒存在。
图6为本实施例的抗菌防紫外线PAN/Ag-TiO2纳米纤维膜中Ag元素和O元素的扫描分布图，进一步证明了Ag和TiO2纳米颗粒都均匀地分布在PAN纳米纤维内部。
可测得本实施例的纳米纤维膜中纳米纤维的平均直径为246nm，纳米纤维膜的平均孔径为2.1μm，孔隙率为92.45%。
根据WS/T 650-2019《抗菌和抑菌效果评价方法》的判定，抑菌率≥90%，产品有较强抑菌作用；根据GB/T 18830-2009《纺织品 防紫外线性能的评定》，当UPF>40, UVA的透射率小于5%时，称为防紫外线产品。图7为纯PAN纳米纤维膜和本实施例抗菌防紫外线PAN/Ag-TiO2纳米纤维膜表面大肠杆菌菌落的培养情况，对比图7（a）和图7（b）可以看出，PAN/Ag-TiO2纳米纤维膜表面的大肠杆菌菌落远少于纯PAN纳米纤维膜。测得本实施例的抗菌防紫外线高效低阻微纳米纤维口罩面料的过滤效率为98.98%，阻力压降为60.76Pa，抑菌率为92.5%，紫外吸防护系数（UPF）为66.03，UVA的透射率为1.64%，表明该抗菌防紫外线高效低阻微纳米纤维口罩面料具有较高的过滤效率、较低的阻力压降以及较强的抑菌作用和紫外吸防护功能。
实施例2
一种抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：向质量分数为13%的PCL纳米纤维溶液（将二氯甲烷和DMF以体积比7:3混合，作为溶剂）中加入粒径为10-50nm的Ag掺杂ZnO光催化复合抗菌剂，Ag掺杂ZnO光催化复合抗菌剂的质量为PCL纳米纤维溶液的质量的1.0%，Ag掺杂ZnO光催化复合抗菌剂中Ag与ZnO的物质的量比为1:1；超声1h，使Ag掺杂ZnO光催化复合抗菌剂均匀地分散在PCL纳米纤维溶液中，然后在室温下搅拌20h，使溶液均匀澄清，再进行消泡，将得到的混合溶液作为纺丝液，备用。
（2）将步骤（1）制得的纺丝液用无针头的静电纺丝机进行静电纺丝。将面密度30g/m2的PP纺粘无纺布卷绕在接收装置上，接收装置的运动速度为1m/min；将纺丝液放置于供液器中，将供液器与无针头喷丝头相连，供液器的流速设为100mL/h，保证纺丝液的供给；在检查电路无误后，打开面板上的高压发生器，将电压调到40kV，喷丝头沿垂直于PP纺粘无纺布的方向往复运动，保证纺丝液均匀地喷覆在PP纺粘无纺布的表面，纺丝1h，制备PP纺粘无纺布-纳米纤维膜。
（3）将步骤（2）制得的PP纺粘无纺布-纳米纤维膜取下，在纳米纤维膜面覆盖上一层20g/m2的黏胶水刺无纺布，利用超声波粘合机进行剪切和粘合，制得抗菌防紫外线高效低阻微纳米纤维口罩面料。
图8为本实施例的抗菌防紫外线PCL/Ag-ZnO纳米纤维膜的SEM图，可测得膜中纳米纤维的平均直径为210.8nm，纳米纤维膜的平均孔径为1.92μm，孔隙率为93.54%。
测得本实施例的抗菌防紫外线高效低阻微纳米纤维口罩面料的过滤效率为99.999%，阻力压降为115Pa，抑菌率为98.39%，紫外吸防护系数（UPF）为110，UVA的透射率为1.1%。
实施例3
一种抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：向质量分数为5%的PU纳米纤维溶液（以DMF作为溶剂）中加入粒径为10-50nm的Ag掺杂ZnO光催化复合抗菌剂，Ag掺杂ZnO光催化复合抗菌剂的质量为PU纳米纤维溶液质量的0.5%，Ag掺杂ZnO光催化复合抗菌剂中Ag与ZnO的物质的量比为0.75:1；超声1.5h，使Ag掺杂ZnO光催化复合抗菌剂均匀地分散在PU纳米纤维溶液中，然后在室温下搅拌18h，使溶液均匀澄清，再进行消泡，将得到的混合溶液作为纺丝液，备用。
（2）将步骤（1）制得的纺丝液用无针头的静电纺丝机进行静电纺丝。将面密度50g/m2的PP纺粘无纺布卷绕在接收装置上，接收装置的运动速度为1m/min；将纺丝液放置于供液器中，将供液器与无针头喷丝头相连，供液器的流速设为150mL/h，保证纺丝液的供给；在检查电路无误后，打开面板上的高压发生器，将电压调到45kV，喷丝头沿垂直于PP纺粘无纺布的方向往复运动，保证纺丝液均匀地喷覆在PP纺粘无纺布的表面，纺丝40min，制备PP纺粘无纺布-纳米纤维膜。
（3）将步骤（2）制得的PP纺粘无纺布-纳米纤维膜取下，在纳米纤维膜面覆盖上一层45g/m2的黏胶水刺无纺布，利用超声波粘合机进行剪切和粘合，制得抗菌防紫外线高效低阻微纳米纤维口罩面料。
测得本实施例纳米纤维膜中纳米纤维的平均直径为358nm，纳米纤维膜的平均孔径为3.08μm，孔隙率为92.25%。测得本实施例的抗菌防紫外线高效低阻微纳米纤维口罩面料的过滤效率为97.56%，阻力压降为56.2Pa，抑菌率为94.5%，紫外吸防护系数（UPF）为51.03，UVA的透射率为3.28%。
实施例4
一种抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：向质量分数为25%的PET纳米纤维溶液（将三氟乙酸和二氯甲烷以体积比4:1混合，作为溶剂）中加入粒径为10-50nm的GO掺杂TiO2光催化复合抗菌剂，GO掺杂TiO2光催化复合抗菌剂的物质的量比为PET纳米纤维溶液的质量的2%，GO掺杂TiO2光催化复合抗菌剂中GO与TiO2的质量比为1:1；超声30min，使GO掺杂TiO2光催化复合抗菌剂均匀地分散在PET纳米纤维溶液中，然后在室温下搅拌24h，使溶液均匀澄清，再进行消泡，将得到的混合溶液作为纺丝液，备用。
（2）将步骤（1）制得的纺丝液用无针头的静电纺丝机进行静电纺丝。将面密度15g/m2的PP纺粘无纺布卷绕在接收装置上，接收装置的运动速度为0.5m/min；将纺丝液放置于供液器中，将供液器与无针头喷丝头相连，供液器的流速设为90mL/h，保证纺丝液的供给；在检查电路无误后，打开面板上的高压发生器，将电压调到45kV，喷丝头沿垂直于PP纺粘无纺布的方向往复运动，保证纺丝液均匀地喷覆在PP纺粘无纺布的表面，纺丝30min，制备PP纺粘无纺布-纳米纤维膜。
（3）将步骤（2）制得的PP纺粘无纺布-纳米纤维膜取下，在纳米纤维膜面覆盖上一层25g/m2的黏胶水刺无纺布，利用超声波粘合机进行剪切和粘合，制得抗菌防紫外线高效低阻微纳米纤维口罩面料。
测得本实施例纳米纤维膜中纳米纤维的平均直径为412nm，纳米纤维膜的平均孔径为3.87μm，孔隙率为91.78%。测得本实施例的抗菌防紫外线高效低阻微纳米纤维口罩面料的过滤效率为92.47%，阻力压降为50Pa，抑菌率为99.27%，紫外吸防护系数（UPF）为79.12，UVA的透射率为1.45%。
实施例5
一种抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：向质量分数为10%的PLLA纳米纤维溶液（将三氯甲烷和DMF以4:1的体积比混合，作为溶剂）中加入粒径为10-50nm的N掺杂MgO光催化复合抗菌剂，N掺杂MgO光催化复合抗菌剂的物质的量比为PLLA纳米纤维溶液的质量的1.5%，N掺杂MgO光催化复合抗菌剂中N与MgO的质量比为0.05:1；超声2h，使N掺杂MgO光催化复合抗菌剂均匀地分散在PLLA纳米纤维溶液中，然后在室温下搅拌8h，使溶液均匀澄清，再进行消泡，将得到的混合溶液作为纺丝液，备用。
（2）将步骤（1）制得的纺丝液用无针头的静电纺丝机进行静电纺丝。将面密度30g/m2的PP纺粘无纺布卷绕在接收装置上，接收装置的运动速度为0.6m/min；将纺丝液放置于供液器中，将供液器与无针头喷丝头相连，供液器的流速设为140mL/h，保证纺丝液的供给；在检查电路无误后，打开面板上的高压发生器，将电压调到60kV，喷丝头沿垂直于PP纺粘无纺布的方向往复运动，保证纺丝液均匀地喷覆在PP纺粘无纺布的表面，纺丝30min，制备PP纺粘无纺布-纳米纤维膜。
（3）将步骤（2）制得的PP纺粘无纺布-纳米纤维膜取下，在纳米纤维膜面覆盖上一层50g/m2的黏胶水刺无纺布，利用超声波粘合机进行剪切和粘合，制得抗菌防紫外线高效低阻微纳米纤维口罩面料。
测得本实施例的纳米纤维膜中纳米纤维的平均直径为485nm，纳米纤维膜的平均孔径为3.97μm，孔隙率为90.47%。测得本实施例的抗菌防紫外线高效低阻微纳米纤维口罩面料的过滤效率为91%，阻力压降为52Pa，抑菌率为98.91%，紫外吸防护系数（UPF）为57，UVA的透射率为1.9%。
实施例6
一种抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，包括以下步骤：
（1）制备纺丝液：向质量分数为12%的PAN纳米纤维溶液（以DMF作为溶剂）中加入粒径为10-50nm的GO掺杂MgO光催化复合抗菌剂，GO掺杂MgO光催化复合抗菌剂的物质的量比为PAN纳米纤维溶液的质量的1.5%，GO掺杂MgO光催化复合抗菌剂中GO与MgO的质量比为1:1；超声20min，使GO掺杂MgO光催化复合抗菌剂均匀地分散在PAN纳米纤维溶液中，然后在室温下搅拌24h，使溶液均匀澄清，再进行消泡，将得到的混合溶液作为纺丝液，备用。
（2）将步骤（1）制得的纺丝液用无针头的静电纺丝机进行静电纺丝。将面密度35g/m2的PP纺粘无纺布卷绕在接收装置上，接收装置的运动速度为0.1m/min；将纺丝液放置于供液器中，将供液器与无针头喷丝头相连，供液器的流速设为50mL/h，保证纺丝液的供给；在检查电路无误后，打开面板上的高压发生器，将电压调到45kV，喷丝头沿垂直于PP纺粘无纺布的方向往复运动，保证纺丝液均匀地喷覆在PP纺粘无纺布的表面，纺丝20min，制备PP纺粘无纺布-纳米纤维膜。
（3）将步骤（2）制得的PP纺粘无纺布-纳米纤维膜取下，在纳米纤维膜面覆盖上一层40g/m2的黏胶水刺无纺布，利用超声波粘合机进行剪切和粘合，制得抗菌防紫外线高效低阻微纳米纤维口罩面料。
图8为本实施例的抗菌防紫外线PCL/GO-MgO纳米纤维膜的SEM图，可测得膜中纳米纤维的平均直径为179nm，纳米纤维膜的平均孔径为1.15μm，孔隙率为92.87%。
测得本实施例的抗菌防紫外线高效低阻微纳米纤维口罩面料的过滤效率为89%，阻力压降为20Pa，抑菌率为89.79%，紫外吸防护系数（UPF）为42，UVA的透射率为3.87%。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种抗菌防紫外线高效低阻微纳米纤维口罩面料，其特征在于：所述抗菌防紫外线高效低阻微纳米纤维口罩面料为三明治结构，包括内层、中间层和外层；所述内层为亲水层，中间层为含有光催化复合抗菌剂的纳米纤维膜，外层为疏水层。
2.根据权利要求1所述的抗菌防紫外线高效低阻微纳米纤维口罩面料，其特征在于：所述亲水层为黏胶水刺无纺布；所述疏水层为PP纺粘无纺布；所述光催化复合抗菌剂均匀分布在纳米纤维膜内部。
3.根据权利要求2所述的抗菌防紫外线高效低阻微纳米纤维口罩面料，其特征在于：所述光催化复合抗菌剂为纳米Ag、纳米氧化石墨烯或纳米非金属离子掺杂的光催化抗菌剂。
4.根据权利要求3所述的抗菌防紫外线高效低阻微纳米纤维口罩面料，其特征在于：所述光催化复合抗菌剂中纳米Ag、纳米氧化石墨烯或纳米非金属离子与光催化抗菌剂的质量比为（0.05-1）：1。
5.根据权利要求4所述的抗菌防紫外线高效低阻微纳米纤维口罩面料，其特征在于：所述纳米非金属离子为纳米S或纳米N；所述光催化抗菌剂为TiO2、ZnO和MgO中的任一种。
6.权利要求1-5任一项所述的抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，其特征在于，包括以下步骤：
（1）用有机溶剂溶解聚合物纳米纤维得到聚合物纳米纤维溶液，向聚合物纳米纤维溶液中加入光催化复合抗菌剂，经超声，然后在室温下搅拌并消泡，得到含有光催化复合抗菌剂的聚合物纳米纤维溶液，作为纺丝液；
（2）将步骤（1）制得的纺丝液进行静电纺丝，以PP纺粘无纺布作为接收基底，制得PP纺粘无纺布-纳米纤维膜；
（3）在步骤（2）的PP纺粘无纺布-纳米纤维膜的纳米纤维膜面上覆盖一层黏胶水刺无纺布，以黏胶水刺无纺布作为内层，经剪切并粘合，得到抗菌防紫外线高效低阻微纳米纤维口罩面料。
7.根据权利要求6所述的抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，其特征在于：所述步骤（1）中有机溶剂为二甲基甲酰胺、三氟乙酸、二氯甲烷和三氯甲烷中的至少一种；所述聚合物纳米纤维为聚丙烯腈纳米纤维、聚氨酯纳米纤维、聚酯纳米纤维、聚乳酸纳米纤维和聚己内酯纳米纤维中的任一种，在聚合物纳米纤维溶液中的质量分数为5-25%；所述光催化复合抗菌剂的粒径为10-50nm、质量为聚合物纳米纤维溶液的质量的0.5-2%；所述超声的时间为20min-2h。
8.根据权利要求7所述的抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，其特征在于，所述步骤（2）中静电纺丝的工艺参数为：高压发生器的电压为40-60kV，纺丝液流量为50-150mL/h，接收时间20min-1h，接收装置以0.1-1m/min的速度运动。
9.根据权利要求8所述的抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，其特征在于：所述步骤（2）纳米纤维膜中纳米纤维的平均直径＜500nm，纳米纤维膜的平均孔径＜4μm、面密度为0.5-10g/m2；PP纺粘无纺布的面密度为15-50g/m2。
10.根据权利要求9所述的抗菌防紫外线高效低阻微纳米纤维口罩面料的制备方法，其特征在于：所述步骤（3）中黏胶水刺无纺布的面密度为20-50g/m2。
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Application publication date: 20221108