CN113622186B - Antibacterial and antiviral protective material and preparation method thereof - Google Patents
Antibacterial and antiviral protective material and preparation method thereof Download PDFInfo
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- CN113622186B CN113622186B CN202110757285.3A CN202110757285A CN113622186B CN 113622186 B CN113622186 B CN 113622186B CN 202110757285 A CN202110757285 A CN 202110757285A CN 113622186 B CN113622186 B CN 113622186B
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- solution
- fabric
- antibacterial
- protective material
- cuprous oxide
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 74
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 59
- 230000001681 protective effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 123
- 239000004744 fabric Substances 0.000 claims abstract description 106
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 18
- 239000012670 alkaline solution Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 50
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- -1 ethyl hydrogen Chemical class 0.000 claims description 21
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- 239000002243 precursor Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
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- 239000008103 glucose Substances 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- VEMHQNXVHVAHDN-UHFFFAOYSA-J [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VEMHQNXVHVAHDN-UHFFFAOYSA-J 0.000 description 1
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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Abstract
本发明提供了一种抗菌抗病毒防护材料及其制备方法。该抗菌抗病毒防护材料的制备方法，首先对织物进行前处理，然后将织物依次浸渍铜源溶液、碱性溶液和还原溶液；最后再将织物置于溶剂中进行原位反应生成纳米氧化亚铜，反应温度为100℃～300℃，反应时间为5s～1800s。通过上述方式，在高温环境下进行原位合成反应，使得织物上的溶剂在原位合成的溶剂中气化，产生瞬时高压，几秒内即可完成纳米氧化亚铜的合成，降温时，得到的纳米氧化亚铜颗粒固定在前处理形成在纤维表面的凹槽中，显著提高了纳米氧化亚铜颗粒与织物的结合牢度，保证了织物的长效抗菌抗病毒性能。
The invention provides an antibacterial and antiviral protective material and a preparation method thereof. The preparation method of the antibacterial and antiviral protective material firstly pre-treats the fabric, and then sequentially immerses the fabric in a copper source solution, an alkaline solution and a reducing solution; finally, the fabric is placed in a solvent for in-situ reaction to generate nano-cuprous oxide , the reaction temperature is 100°C to 300°C, and the reaction time is 5s to 1800s. Through the above method, the in-situ synthesis reaction is carried out in a high-temperature environment, so that the solvent on the fabric is vaporized in the in-situ synthesis solvent, and instantaneous high pressure is generated, and the synthesis of nano-cuprous oxide can be completed within a few seconds. When the temperature is lowered, the obtained The nano-cuprous oxide particles are fixed in the grooves formed on the fiber surface by pre-treatment, which significantly improves the bonding fastness between the nano-cuprous oxide particles and the fabric, and ensures the long-term antibacterial and antiviral properties of the fabric.
Description
技术领域Technical Field
本发明涉及抗菌抗病毒材料技术领域，尤其涉及一种在织物上原位合成纳米氧化亚铜的抗菌抗病毒防护材料及其制备方法。The invention relates to the technical field of antibacterial and antiviral materials, and in particular to an antibacterial and antiviral protective material for in-situ synthesizing nano cuprous oxide on fabric and a preparation method thereof.
背景技术Background Art
一般纺织品的纤维本身不具有抗菌能力，在一定条件下会给细菌提供生存和繁殖的环境，威胁人类健康。当今社会极端环境、环境污染等生态大环境严重恶化，密闭空间等特殊生存微环境导致人们对功能防护纺织品迫切需求。现有技术中，解决纤维抗菌问题的主要方法是利用具有抗菌作用的纳米粒子与聚合物基体进行复合改性，制备具有抗菌作用的改性纤维，通过纤维在使用过程中逐步释放抗菌成分，达到抗菌的目的。The fibers of general textiles themselves do not have antibacterial ability. Under certain conditions, they will provide an environment for bacteria to survive and reproduce, threatening human health. In today's society, the ecological environment such as extreme environment and environmental pollution has seriously deteriorated, and special living microenvironments such as confined spaces have led to an urgent need for functional protective textiles. In the prior art, the main method to solve the problem of fiber antibacterial is to use nanoparticles with antibacterial effects and polymer matrices for composite modification to prepare modified fibers with antibacterial effects, and gradually release antibacterial components during use of the fibers to achieve the purpose of antibacterial.
相较于纳米银系抗菌剂，铜系抗菌材料具有原料成本较低的优势。现有技术中，织物表面合成氧化亚铜的方式目前采用的一般都是改性或者接枝活性官能团，然后表面合成功能性纳米粒子。但是，现有技术存在负载量低、反应时间长、生产成本高、功能性纳米粒子与织物的结合牢度差、耐洗性差等缺陷，难以满足目前市场的广泛需求。Compared with nanosilver antibacterial agents, copper antibacterial materials have the advantage of lower raw material costs. In the prior art, the method of synthesizing cuprous oxide on the surface of fabrics is generally to modify or graft active functional groups, and then synthesize functional nanoparticles on the surface. However, the prior art has the defects of low loading capacity, long reaction time, high production cost, poor bonding fastness between functional nanoparticles and fabrics, and poor washability, which makes it difficult to meet the wide demand of the current market.
公开号为CN103167798 A的专利提供了一种抗微生物和抗病毒组合物。该抗微生物和抗病毒组合物含有BET比表面积为5-100m2/g的氧化亚铜颗粒和具有醛基的糖，其中具有醛基的糖的含量基于100质量份的氧化亚铜颗粒计算为0.5至10质量份。该组合物通过添加适量的具有醛基的糖以抑制氧化亚铜氧化，以保持良好的抗微生物和抗病毒性质。The patent with publication number CN103167798 A provides an antimicrobial and antiviral composition. The antimicrobial and antiviral composition contains cuprous oxide particles with a BET specific surface area of 5-100 m2 /g and sugar with an aldehyde group, wherein the content of the sugar with an aldehyde group is 0.5 to 10 parts by mass based on 100 parts by mass of the cuprous oxide particles. The composition inhibits the oxidation of cuprous oxide by adding an appropriate amount of sugar with an aldehyde group to maintain good antimicrobial and antiviral properties.
公开号为CN105311668 A的专利提供了一种细菌纤维素复合氧化亚铜抗菌敷料及其制备方法，细菌纤维素复合氧化亚铜抗菌敷料是在细菌纤维素水凝胶膜的三维多孔网络结构中附着氧化亚铜颗粒；氧化亚铜颗粒为八面体晶型，所述抗菌敷料是通过将含有葡萄糖溶液的细菌纤维素水凝胶膜浸泡在NaOH水溶液和铜离子水溶液的混合溶液中，加热加压反应得到的。The patent with publication number CN105311668 A provides a bacterial cellulose composite cuprous oxide antibacterial dressing and a preparation method thereof. The bacterial cellulose composite cuprous oxide antibacterial dressing is a three-dimensional porous network structure of a bacterial cellulose hydrogel film in which cuprous oxide particles are attached; the cuprous oxide particles are octahedral crystals, and the antibacterial dressing is obtained by immersing a bacterial cellulose hydrogel film containing a glucose solution in a mixed solution of a NaOH aqueous solution and a copper ion aqueous solution, and heating and pressurizing the reaction.
但是，采用在织物/纤维上负载氧化亚铜颗粒赋予织物抗菌性能，存在负载量有限、结合牢度差的问题；在织物表面合成功能性粒子的方法存在反应时间长、反应过程复杂、生产成本高的问题。However, the method of loading cuprous oxide particles on fabrics/fibers to give fabrics antibacterial properties has the problems of limited loading capacity and poor binding fastness; the method of synthesizing functional particles on the surface of fabrics has the problems of long reaction time, complex reaction process and high production cost.
有鉴于此，有必要设计一种改进的包含有纳米氧化亚铜的抗菌抗病毒防护材料及其制备方法，以解决上述问题。In view of this, it is necessary to design an improved antibacterial and antiviral protective material containing nano cuprous oxide and a preparation method thereof to solve the above problems.
发明内容Summary of the invention
针对上述现有技术的缺陷，本发明的目的在于提供一种合成方法简单、且能够快速在织物上原位合成纳米氧化亚铜的抗菌抗病毒防护材料的制备方法，并且得到的抗菌抗病毒防护材料中的纳米氧化亚铜与织物的结合牢度高、耐洗性良好，具有长效抗菌抗病毒性能，满足市场的广泛需求。In view of the defects of the above-mentioned prior art, the purpose of the present invention is to provide a method for preparing an antibacterial and antiviral protective material with a simple synthesis method and capable of quickly synthesizing nano cuprous oxide in situ on fabrics, and the nano cuprous oxide in the obtained antibacterial and antiviral protective material has high bonding strength with the fabric and good washability, and has long-lasting antibacterial and antiviral properties, thereby meeting the wide needs of the market.
为实现上述目的，本发明提供了一种抗菌抗病毒防护材料的制备方法，包括以下步骤：To achieve the above object, the present invention provides a method for preparing an antibacterial and antiviral protective material, comprising the following steps:
S1.织物前处理S1. Fabric pretreatment
将织物置于前处理溶液中浸轧；其中，所述前处理溶液为氢氧化钠溶液、氢氧化钾溶液、氢氧化钠和尿素的混合溶液、生物酶溶液、N-甲基吗啉-N-氧化物溶液、壳聚糖溶液或者等离子体溶液；The fabric is placed in a pretreatment solution for padding; wherein the pretreatment solution is a sodium hydroxide solution, a potassium hydroxide solution, a mixed solution of sodium hydroxide and urea, a biological enzyme solution, an N-methylmorpholine-N-oxide solution, a chitosan solution or a plasma solution;
S2.前处理织物浸渍前驱体溶液S2. Pre-treatment of fabrics by impregnation with precursor solution
将前处理后的织物依次浸渍碱性溶液、铜源溶液和还原溶液，浸渍时间为5s～360s；其中，所述铜源溶液中溶质的质量分数为0.1％～20％；所述碱性溶液中溶质的质量分数为0.1％～20％；所述还原溶液中溶质的质量分数为0.1％～20％；The pre-treated fabric is sequentially immersed in an alkaline solution, a copper source solution and a reducing solution for 5 seconds to 360 seconds; wherein the mass fraction of the solute in the copper source solution is 0.1% to 20%; the mass fraction of the solute in the alkaline solution is 0.1% to 20%; and the mass fraction of the solute in the reducing solution is 0.1% to 20%;
S3.织物原位合成氧化亚铜S3. In-situ synthesis of cuprous oxide on fabrics
将浸渍前驱体溶液后的织物置于溶剂中进行反应原位生成氧化亚铜，反应温度为100℃～300℃，反应时间为5s～1800s；The fabric impregnated with the precursor solution is placed in a solvent for reaction to generate cuprous oxide in situ, the reaction temperature is 100° C. to 300° C., and the reaction time is 5 s to 1800 s;
所述溶剂为乙二醇、丙三醇、乙酸乙酯、甲苯、二甲苯、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、硅油、植物油、动物油。The solvent is ethylene glycol, glycerol, ethyl acetate, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, silicone oil, vegetable oil, and animal oil.
作为本发明的进一步改进，在步骤S2中，所述铜源溶液为醋酸铜溶液、硝酸铜溶液、硫酸铜溶液或者氯化铜溶液；所述碱性溶液为氢氧化钠溶液、氢氧化钾溶液、碳酸铵溶液或者氨水溶液；所述还原溶液为败坏血酸溶液、葡萄糖溶液、一缩二乙二醇或者丙三醇溶液。As a further improvement of the present invention, in step S2, the copper source solution is a copper acetate solution, a copper nitrate solution, a copper sulfate solution or a copper chloride solution; the alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, an ammonium carbonate solution or an ammonia solution; and the reducing solution is an ascorbic acid solution, a glucose solution, a diethylene glycol solution or a glycerol solution.
作为本发明的进一步改进，所述硅油为甲基硅油、乙基硅油、乙基含氢硅油、苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油或者含氟硅油。As a further improvement of the present invention, the silicone oil is methyl silicone oil, ethyl silicone oil, ethyl hydrogen silicone oil, phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil or fluorine-containing silicone oil.
作为本发明的进一步改进，在步骤S1中，所述前处理溶液中溶质的质量分数为0.1％～20％；或者，在步骤S1中，浸渍温度为-12℃～80℃，浸轧后织物的带液率为10％～160％，所述浸轧方式为一浸一轧或二浸二轧或三浸三轧。As a further improvement of the present invention, in step S1, the mass fraction of the solute in the pretreatment solution is 0.1% to 20%; or, in step S1, the immersion temperature is -12°C to 80°C, the liquid carrying rate of the fabric after immersion and padding is 10% to 160%, and the immersion and padding method is one immersion and one padding, two immersions and two paddings, or three immersions and three paddings.
作为本发明的进一步改进，在步骤S2中，所述浸轧方式为一浸一轧或二浸二轧或三浸三轧；浸渍温度为10℃～80℃，浸轧后织物的带液率为10％～160％。As a further improvement of the present invention, in step S2, the dipping and rolling method is one dipping and one rolling, two dipping and two rolling, or three dipping and three rolling; the dipping temperature is 10°C to 80°C, and the liquid carrying rate of the fabric after dipping and rolling is 10% to 160%.
作为本发明的进一步改进，还包括后处理步骤，将步骤S3得到的织物进行洗涤以除去溶剂。As a further improvement of the present invention, a post-treatment step is also included, in which the fabric obtained in step S3 is washed to remove the solvent.
为实现上述目的，本发明还提供了一种抗菌抗病毒防护材料，该抗菌抗病毒防护材料为经纳米氧化亚铜改性的织物；所述纳米氧化亚铜经前驱体溶液原位反应生成，且均匀分布于所述抗菌抗病毒防护材料的纤维的内部和外部，所述纳米氧化亚铜的粒径为50nm-600nm。To achieve the above-mentioned purpose, the present invention also provides an antibacterial and antiviral protective material, which is a fabric modified with nano-cuprous oxide; the nano-cuprous oxide is generated by in-situ reaction of a precursor solution and is evenly distributed inside and outside the fibers of the antibacterial and antiviral protective material, and the particle size of the nano-cuprous oxide is 50nm-600nm.
作为本发明的进一步改进，所述纳米氧化亚铜的晶型为立方体型、八面体型、菱形十二面体型、十八面体型、二十六面体型中的一种或多种。As a further improvement of the present invention, the crystal form of the nano cuprous oxide is one or more of a cubic form, an octahedral form, a rhombic dodecahedral form, an octahedral form, and an icosahedral form.
作为本发明的进一步改进，所述织物具有杀菌杀病毒性能；所述抗菌抗病毒防护材料应用于制备口罩、防毒面具、防护服、空气净化器或者空气滤芯。As a further improvement of the present invention, the fabric has bactericidal and antiviral properties; the antibacterial and antiviral protective material is used to prepare masks, gas masks, protective clothing, air purifiers or air filter elements.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明通过选用合适的前处理溶液对织物进行微溶解前处理，使得纤维表面形成凹槽，为后续原位合成反应提供若干个反应空间；即，为后续纳米氧化亚铜粒子提供生长位置；然后将织物依次浸渍铜源溶液、碱性溶液和还原溶液；然后再将织物置于溶剂中进行反应生成氧化亚铜，反应温度为100℃～300℃，反应时间为5s～1800s；该原位合成过程中，基于在前面的浸轧步骤中控制浸轧后织物的带液率为10％～160％，使得织物上带有溶剂，在高温环境下(100℃～300℃)进行原位合成反应时，织物上的溶剂在原位合成的溶剂中气化，产生瞬时高压，几秒内即可完成纳米氧化亚铜的合成，降温时，得到的纳米氧化亚铜颗粒固定在前处理形成在纤维表面的凹槽中，显著提高了纳米氧化亚铜颗粒与织物的结合牢度，保证了织物的长效抗菌抗病毒性能。(1) The present invention performs micro-dissolution pretreatment on the fabric by selecting a suitable pretreatment solution, so that grooves are formed on the fiber surface, providing a plurality of reaction spaces for the subsequent in-situ synthesis reaction; that is, providing a growth position for the subsequent nano cuprous oxide particles; then the fabric is sequentially immersed in a copper source solution, an alkaline solution and a reducing solution; and then the fabric is placed in a solvent for reaction to generate cuprous oxide, the reaction temperature is 100° C. to 300° C., and the reaction time is 5s to 1800s; in the in-situ synthesis process, based on the control of the liquid carrying rate of the fabric after padding to 10% to 160% in the previous padding step, the fabric is provided with solvent, when the in-situ synthesis reaction is performed under a high temperature environment (100° C. to 300° C.), the solvent on the fabric is vaporized in the in-situ synthesized solvent, generating instantaneous high pressure, and the synthesis of nano cuprous oxide can be completed within a few seconds, and when the temperature is lowered, the obtained nano cuprous oxide particles are fixed in the grooves formed on the fiber surface by the pretreatment, which significantly improves the bonding strength between the nano cuprous oxide particles and the fabric, and ensures the long-term antibacterial and antiviral properties of the fabric.
(2)本发明制备的抗菌抗病毒防护材料的抗菌性能优异：对细菌和病毒的杀伤率高达99％，可用于口罩、防护服、面罩、空气净化方面等抗菌材料领域。(2) The antibacterial and antiviral protective material prepared by the present invention has excellent antibacterial properties: the killing rate of bacteria and viruses is as high as 99%, and can be used in the field of antibacterial materials such as masks, protective clothing, face masks, and air purification.
(3)本发明的抗菌抗病毒防护材料的制备方法，首先通过预处理在纤维表面形成反应空间，然后将反应材料浸渍在织物上，然后在高温溶剂中进行原位合成反应，快速简便的合成氧化亚铜纳米粒子，降温时纳米粒子牢度固定在纤维上，该制备方法操作简单，使用范围广，降低了生产成本，具有较高的应用价值。(3) The preparation method of the antibacterial and antiviral protective material of the present invention first forms a reaction space on the fiber surface through pretreatment, then impregnates the reaction material on the fabric, and then performs an in-situ synthesis reaction in a high-temperature solvent to quickly and easily synthesize cuprous oxide nanoparticles. When the temperature is lowered, the nanoparticles are firmly fixed on the fiber. The preparation method is simple to operate, has a wide range of applications, reduces production costs, and has high application value.
(4)本发明的制备方法，可以通过调控温度以在织物上合成不同晶型的氧化亚铜纳米粒子，以满足不同需要，适用范围广。(4) The preparation method of the present invention can synthesize cuprous oxide nanoparticles of different crystal forms on fabrics by adjusting the temperature to meet different needs and has a wide range of applications.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明的实施例1制备的抗菌抗病毒防护材料的电镜图，标尺为10um。FIG1 is an electron microscope image of the antibacterial and antiviral protective material prepared in Example 1 of the present invention, with a scale of 10 um.
图2为本发明的实施例1制备的抗菌抗病毒防护材料的电镜图，标尺为1um。FIG2 is an electron microscope image of the antibacterial and antiviral protective material prepared in Example 1 of the present invention, with a scale of 1 um.
图3为本发明的实施例1制备的抗菌抗病毒防护材料的电镜图，标尺为1um。FIG3 is an electron microscope image of the antibacterial and antiviral protective material prepared in Example 1 of the present invention, with a scale of 1 um.
图4为本发明的实施例1制备的抗菌抗病毒防护材料的能谱分析图。FIG. 4 is an energy spectrum analysis diagram of the antibacterial and antiviral protective material prepared in Example 1 of the present invention.
图5为本发明的实施例1制备的抗菌抗病毒防护材料的元素分布图。FIG5 is an element distribution diagram of the antibacterial and antiviral protective material prepared in Example 1 of the present invention.
图6为本发明的实施例1制备的抗菌抗病毒防护材料的抗菌测试结果图。FIG6 is a graph showing the antibacterial test results of the antibacterial and antiviral protective material prepared in Example 1 of the present invention.
图7为本发明的实施例13制备的抗菌抗病毒防护材料的电镜图，标尺为1um。FIG7 is an electron microscope image of the antibacterial and antiviral protective material prepared in Example 13 of the present invention, with a scale of 1 um.
具体实施方式DETAILED DESCRIPTION
为了使本发明的目的、技术方案和优点更加清楚，下面结合附图和具体实施例对本发明进行详细描述。In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
在此，还需要说明的是，为了避免因不必要的细节而模糊了本发明，在附图中仅仅示出了与本发明的方案密切相关的结构和/或处理步骤，而省略了与本发明关系不大的其他细节。It should also be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to the scheme of the present invention are shown in the drawings, while other details that are not closely related to the present invention are omitted.
另外，还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。In addition, it should be noted that the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.
本发明提供了一种抗菌抗病毒防护材料的制备方法，包括以下步骤：The present invention provides a method for preparing an antibacterial and antiviral protective material, comprising the following steps:
S1.织物前处理S1. Fabric pretreatment
将织物置于前处理溶液中浸轧；其中，所述前处理溶液为氢氧化钠溶液、氢氧化钾溶液、氢氧化钠和尿素的混合溶液、生物酶溶液、N-甲基吗啉-N-氧化物溶液、壳聚糖溶液或者等离子体溶液；The fabric is placed in a pretreatment solution for padding; wherein the pretreatment solution is a sodium hydroxide solution, a potassium hydroxide solution, a mixed solution of sodium hydroxide and urea, a biological enzyme solution, an N-methylmorpholine-N-oxide solution, a chitosan solution or a plasma solution;
S2.前处理织物浸渍前驱体溶液S2. Pre-treatment of fabrics by impregnation with precursor solution
将前处理后的织物依次浸渍碱性溶液、铜源溶液和还原溶液，浸渍时间为5s～360s；其中，所述铜源溶液中溶质的质量分数为0.1％～20％；所述碱性溶液中溶质的质量分数为0.1％～20％；所述还原溶液中溶质的质量分数为0.1％～20％；The pre-treated fabric is sequentially immersed in an alkaline solution, a copper source solution and a reducing solution for 5 seconds to 360 seconds; wherein the mass fraction of the solute in the copper source solution is 0.1% to 20%; the mass fraction of the solute in the alkaline solution is 0.1% to 20%; and the mass fraction of the solute in the reducing solution is 0.1% to 20%;
S3.织物原位合成氧化亚铜S3. In-situ synthesis of cuprous oxide on fabrics
将浸渍前驱体溶液后的织物置于溶剂中进行反应原位生成氧化亚铜，反应温度为100℃～300℃，反应时间为5s～1800s；The fabric impregnated with the precursor solution is placed in a solvent for reaction to generate cuprous oxide in situ, the reaction temperature is 100° C. to 300° C., and the reaction time is 5 s to 1800 s;
所述溶剂为乙二醇、丙三醇、乙酸乙酯、甲苯、二甲苯、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、硅油、植物油、动物油。所述硅油为甲基硅油、乙基硅油、乙基含氢硅油、苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油或者含氟硅油。The solvent is ethylene glycol, glycerol, ethyl acetate, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, silicone oil, vegetable oil, animal oil. The silicone oil is methyl silicone oil, ethyl silicone oil, ethyl hydrogen silicone oil, phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil or fluorine-containing silicone oil.
在步骤S1中，所述前处理溶液中溶质的质量分数为0.1％～20％；浸渍温度为-12℃～80℃，浸轧后织物的带液率为10％～160％，所述浸轧方式为一浸一轧或二浸二轧或三浸三轧。In step S1, the mass fraction of the solute in the pretreatment solution is 0.1% to 20%; the immersion temperature is -12°C to 80°C, the liquid carrying rate of the fabric after padding is 10% to 160%, and the padding method is one dip and one padding, two dips and two paddings, or three dips and three paddings.
在步骤S2中，所述铜源溶液为醋酸铜溶液、硝酸铜溶液、硫酸铜溶液或者氯化铜溶液；所述碱性溶液为氢氧化钠溶液、氢氧化钾溶液、碳酸铵溶液或者氨水溶液；所述还原溶液为败坏血酸溶液、葡萄糖溶液、一缩二乙二醇或者丙三醇溶液。In step S2, the copper source solution is copper acetate solution, copper nitrate solution, copper sulfate solution or copper chloride solution; the alkaline solution is sodium hydroxide solution, potassium hydroxide solution, ammonium carbonate solution or ammonia solution; the reducing solution is ascorbic acid solution, glucose solution, diethylene glycol or glycerol solution.
所述浸轧方式为一浸一轧或二浸二轧或三浸三轧；浸渍温度为10℃～80℃，浸轧后织物的带液率为10％～160％。The padding method is one dip and one padding, two dips and two paddings, or three dips and three paddings; the dipping temperature is 10° C. to 80° C., and the liquid carrying rate of the fabric after padding is 10% to 160%.
应当理解，该制备方法还可以包括后处理步骤，将步骤S3得到的织物进行洗涤以除去溶剂。It should be understood that the preparation method may further include a post-treatment step of washing the fabric obtained in step S3 to remove the solvent.
需要说明的是，所述织物为机织物、针织物或者无纺布；所述织物由天然纤维或者合成纤维中的一种或多种织造而成；所述天然纤维为棉纤维、麻纤维、蚕丝纤维、羊毛纤维、木棉纤维或者灯心草纤维；所述合成纤维为涤纶纤维、锦纶纤维、腈纶纤维、维纶纤维、丙纶纤维或者氯纶纤维。It should be noted that the fabric is a woven fabric, a knitted fabric or a non-woven fabric; the fabric is woven from one or more natural fibers or synthetic fibers; the natural fibers are cotton fibers, linen fibers, silk fibers, wool fibers, kapok fibers or rush fibers; the synthetic fibers are polyester fibers, nylon fibers, acrylic fibers, vinylon fibers, polypropylene fibers or chloroprene fibers.
所述织造方式包括纺纱、机织、针织、熔喷或者针刺。The weaving methods include spinning, weaving, knitting, melt-blowing or needle punching.
下面结合实施例及对比例对本发明提供的抗菌抗病毒防护材料的制备方法进行说明。The preparation method of the antibacterial and antiviral protective material provided by the present invention is described below in conjunction with embodiments and comparative examples.
实施例1Example 1
本实施例提供了一种抗菌抗病毒防护材料的制备方法，包括如下步骤：This embodiment provides a method for preparing an antibacterial and antiviral protective material, comprising the following steps:
S1.织物前处理S1. Fabric pretreatment
将丙纶织物置于质量分数为7％的氢氧化钠溶液中浸轧；其中，浸渍时间为5s，浸渍温度为25℃，浸轧后织物的带液率为120％，所述的浸轧为一浸一轧或二浸二轧或三浸三轧；The polypropylene fabric is placed in a sodium hydroxide solution with a mass fraction of 7% and is padded; wherein the immersion time is 5 seconds, the immersion temperature is 25° C., the liquid carrying rate of the fabric after padded is 120%, and the padded process is one dip and one padded, two dips and two padded, or three dips and three padded;
S2.前处理织物浸渍前驱体溶液S2. Pre-treatment of fabrics by impregnation with precursor solution
将前处理后的丙纶织物依次浸渍质量分数为7％的氢氧化钠碱性溶液60s、质量分数为4％的硫酸铜溶液30s和质量分数为4％的葡萄糖还原溶液300s；The pretreated polypropylene fabric was immersed in a 7% sodium hydroxide alkaline solution for 60 seconds, a 4% copper sulfate solution for 30 seconds, and a 4% glucose reducing solution for 300 seconds.
S3.织物原位合成氧化亚铜S3. In-situ synthesis of cuprous oxide on fabrics
将浸渍前驱体溶液后的织物置于温度为150℃的二甲基硅油溶剂中进行反应原位生成氧化亚铜，反应时间为15s；即，得到包含有纳米氧化亚铜颗粒的抗菌抗病毒防护材料。The fabric immersed in the precursor solution is placed in a dimethyl silicone oil solvent at a temperature of 150° C. to react and generate cuprous oxide in situ, and the reaction time is 15 seconds; that is, an antibacterial and antiviral protective material containing nano cuprous oxide particles is obtained.
对实施例1制备的抗菌抗病毒防护材料进行扫描电镜表征，结果如图1-3所示。由图1-3可以看出，在纤维表面均匀负载了大量纳米粒子，表明本发明提供的制备方法能够将纳米粒子原位合成并均匀地负载于纤维表面。The antibacterial and antiviral protective material prepared in Example 1 was characterized by scanning electron microscopy, and the results are shown in Figures 1 to 3. As can be seen from Figures 1 to 3, a large number of nanoparticles are uniformly loaded on the fiber surface, indicating that the preparation method provided by the present invention can synthesize nanoparticles in situ and uniformly load them on the fiber surface.
对实施例1制备的抗菌抗病毒防护材料进行EDS能谱分析，结果如图4所示，可见抗菌抗病毒防护材料上含有16wt％的氧原子，11.6wt％的铜原子，表明丙纶织物表面已经成功原位合成Cu2O。图5为其元素分布图，可见，Cu元素分布很均匀，进一步说明Cu2O分布很均匀。The antibacterial and antiviral protective material prepared in Example 1 was subjected to EDS spectrum analysis, and the results are shown in Figure 4. It can be seen that the antibacterial and antiviral protective material contains 16wt% oxygen atoms and 11.6wt% copper atoms, indicating that Cu 2 O has been successfully synthesized in situ on the surface of the polypropylene fabric. Figure 5 is its element distribution diagram, and it can be seen that the Cu element is evenly distributed, further indicating that the Cu 2 O is evenly distributed.
参照GN/T 20944-2008对所述抗菌抗病毒防护材料水洗30次后，参照标准ISO18184:2014(E)对其进行抗菌测试，其对大肠杆菌和金黄色葡萄球菌的杀菌率高达99.9％。After washing the antibacterial and antiviral protective material 30 times with water according to GN/T 20944-2008, an antibacterial test was performed on it according to standard ISO18184:2014(E), and the sterilization rate of the antibacterial and antiviral protective material against Escherichia coli and Staphylococcus aureus was as high as 99.9%.
实施例2～4及对比例1Examples 2 to 4 and Comparative Example 1
实施例2～4分别提供了一种抗菌抗病毒防护材料的制备方法，与实施例1相比，不同之处在于改变了步骤S1浸轧处理后织物的带液率，各实施例对应的制备参数如表1所示。实施例2～4及对比例1的其余步骤均与实施例1基本一致，在此不再赘述。Examples 2 to 4 respectively provide a method for preparing an antibacterial and antiviral protective material. Compared with Example 1, the difference is that the liquid carrying rate of the fabric after the padding treatment in step S1 is changed. The preparation parameters corresponding to each example are shown in Table 1. The remaining steps of Examples 2 to 4 and Comparative Example 1 are basically the same as those of Example 1, and will not be repeated here.
表1实施例2～4及对比例1的步骤S1的浸轧处理后织物的带液率及制备的抗菌抗病毒防护材料的测试结果Table 1 Test results of the liquid carrying rate of the fabric after the padding treatment in step S1 of Examples 2 to 4 and Comparative Example 1 and the prepared antibacterial and antiviral protective materials
比较实施例1-4可知，随着浸轧处理后织物的带液率的增加，纳米氧化亚铜的负载量呈现先增加后减小的趋势，在带液率为120％时，纳米氧化亚铜的负载量最大。Comparing Examples 1-4, it can be seen that as the liquid carrying rate of the fabric after padding increases, the loading amount of nano-cuprous oxide increases first and then decreases. When the liquid carrying rate is 120%, the loading amount of nano-cuprous oxide is the largest.
实验发现，当浸轧处理后织物的带液率小于10％时，不利于反应溶液的负载，因此氧化亚铜的生成负载量较小。Experiments have shown that when the liquid carrying rate of the fabric after padding treatment is less than 10%, it is not conducive to the loading of the reaction solution, so the generated loading amount of cuprous oxide is small.
当浸轧处理后织物的带液率大于120％时，由于负载的反应溶液过大，也不利于氧化亚铜的成长。When the liquid carrying rate of the fabric after padding treatment is greater than 120%, the growth of cuprous oxide is not favorable due to the excessive amount of loaded reaction solution.
实施例5～8
实施例5～8分别提供了一种抗菌抗病毒防护材料的制备方法，与实施例1相比，不同之处在于改变了步骤S1中前处理溶液中溶质的质量分数，各实施例对应的前处理溶液中溶质的质量分数如表2所示。实施例5～8的其余步骤均与实施例1基本一致，在此不再赘述。Examples 5 to 8 respectively provide a method for preparing an antibacterial and antiviral protective material. Compared with Example 1, the difference is that the mass fraction of the solute in the pretreatment solution in step S1 is changed. The mass fraction of the solute in the pretreatment solution corresponding to each embodiment is shown in Table 2. The remaining steps of Examples 5 to 8 are basically the same as those of Example 1 and are not repeated here.
表2实施例5～8的工艺参数及制备的抗菌抗病毒防护材料的测试结果Table 2 Process parameters of Examples 5 to 8 and test results of the prepared antibacterial and antiviral protective materials
实验发现，当前处理溶液中溶质的质量分数小于0.1％时，织物上带有的碱性溶液太少，经后续反应后不足以在织物上形成明显的抗菌抗病毒的效果。Experiments have found that when the mass fraction of the solute in the current treatment solution is less than 0.1%, the amount of alkaline solution on the fabric is too little, and after subsequent reactions, it is not enough to form an obvious antibacterial and antiviral effect on the fabric.
当前处理溶液中溶质的质量分数大于20％时，经过硫酸铜溶液反应后，织物表层负载量太大，负载反应沉淀容易从织物表层脱落，经后续反应后不足以在织物上形成明显的抗菌抗病毒的效果。When the mass fraction of the solute in the current treatment solution is greater than 20%, after the reaction with the copper sulfate solution, the load on the surface of the fabric is too large, and the load reaction precipitate is easily fallen off from the surface of the fabric, which is not enough to form an obvious antibacterial and antiviral effect on the fabric after subsequent reaction.
实施例9～12Examples 9 to 12
实施例9～12分别提供了一种抗菌抗病毒防护材料的制备方法，与实施例1相比，不同之处在于改变了步骤S3中原位合成反应的反应温度和步骤S2中铜源溶液、碱性溶液、还原溶液的质量分数，具体如表3所示。实施例9～12的其余步骤均与实施例1基本一致，在此不再赘述。Examples 9 to 12 respectively provide a method for preparing an antibacterial and antiviral protective material, which is different from Example 1 in that the reaction temperature of the in-situ synthesis reaction in step S3 and the mass fractions of the copper source solution, alkaline solution, and reducing solution in step S2 are changed, as shown in Table 3. The remaining steps of Examples 9 to 12 are basically the same as those of Example 1 and are not described here.
表2实施例9～12的工艺参数Table 2 Process parameters of Examples 9 to 12
实验发现，反应溶液浓度越高，温度越高生成的氧化亚铜纳米粒子的形状越接近球形。Experiments have found that the higher the concentration of the reaction solution and the higher the temperature, the closer the shape of the generated cuprous oxide nanoparticles is to a spherical shape.
需要说明的是，所述溶剂还可以为乙二醇、丙三醇、乙酸乙酯、甲苯、二甲苯、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、硅油、植物油、动物油。所述硅油为甲基硅油、乙基硅油、乙基含氢硅油、苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油或者含氟硅油。It should be noted that the solvent may also be ethylene glycol, glycerol, ethyl acetate, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, silicone oil, vegetable oil, animal oil. The silicone oil may be methyl silicone oil, ethyl silicone oil, ethyl hydrogen silicone oil, phenyl silicone oil, methylchlorophenyl silicone oil, methylethoxy silicone oil, methyltrifluoropropyl silicone oil, methylvinyl silicone oil or fluorine-containing silicone oil.
所述铜源溶液为醋酸铜溶液、硝酸铜溶液、硫酸铜溶液或者氯化铜溶液；所述碱性溶液为氢氧化钠溶液、氢氧化钾溶液、碳酸铵溶液或者氨水溶液；所述还原溶液为败坏血酸溶液、葡萄糖溶液、一缩二乙二醇或者丙三醇溶液。The copper source solution is a copper acetate solution, a copper nitrate solution, a copper sulfate solution or a copper chloride solution; the alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, an ammonium carbonate solution or an ammonia solution; and the reducing solution is an ascorbic acid solution, a glucose solution, a diethylene glycol solution or a glycerol solution.
实施例13Example 13
本实施例提供了一种抗菌抗病毒防护材料的制备方法，包括如下步骤：This embodiment provides a method for preparing an antibacterial and antiviral protective material, comprising the following steps:
S1.织物前处理S1. Fabric pretreatment
将棉织物置于质量分数为7％氢氧化钠和12％的尿素混合溶液中浸泡后浸轧；其中，浸渍时间为2h，浸轧时间为15s，浸渍温度为-12℃，浸轧温度为25℃，浸轧后织物的带液率为150％，所述的浸轧为一浸一轧或二浸二轧或三浸三轧；The cotton fabric is immersed in a mixed solution of 7% sodium hydroxide and 12% urea by mass, and then padded; wherein the immersion time is 2 hours, the padding time is 15 seconds, the immersion temperature is -12°C, the padding temperature is 25°C, the liquid carrying rate of the fabric after padding is 150%, and the padding is one immersion and one padding, two immersions and two paddings, or three immersions and three paddings;
S2.前处理织物浸渍前驱体溶液S2. Pre-treatment of fabrics by impregnation with precursor solution
将前处理后的棉织物依次浸渍质量分数为7％的氢氧化钠碱性溶液5s、质量分数为4％的硫酸铜铜源溶液15s和质量分数为6％的葡萄糖还原溶液300s；The pretreated cotton fabric was sequentially immersed in a 7% sodium hydroxide alkaline solution for 5 seconds, a 4% copper sulfate copper source solution for 15 seconds, and a 6% glucose reducing solution for 300 seconds.
S3.织物原位合成氧化亚铜S3. In-situ synthesis of cuprous oxide on fabrics
将浸渍前驱体溶液后的织物置于温度为200℃的二甲基硅油溶剂中进行反应原位生成氧化亚铜，反应时间为20s；即，得到包含有纳米氧化亚铜颗粒的抗菌抗病毒防护材料。The fabric impregnated with the precursor solution is placed in a dimethyl silicone oil solvent at a temperature of 200° C. to react and generate cuprous oxide in situ, and the reaction time is 20 seconds; that is, an antibacterial and antiviral protective material containing nano cuprous oxide particles is obtained.
对实施例13制备的抗菌抗病毒防护材料进行扫描电镜表征，结果如图7所示。由图7可以看出，在纤维表面均匀负载了大量纳米粒子，表明本发明提供的制备方法能够快速将纳米粒子原位合成并均匀地负载于纤维表面。The antibacterial and antiviral protective material prepared in Example 13 was characterized by scanning electron microscopy, and the results are shown in Figure 7. As can be seen from Figure 7, a large number of nanoparticles are uniformly loaded on the fiber surface, indicating that the preparation method provided by the present invention can quickly synthesize nanoparticles in situ and uniformly load them on the fiber surface.
综上所述，本发明提供的抗菌抗病毒防护材料的制备方法，通过选用合适的前处理溶液对织物进行微溶解前处理，使得纤维表面形成凹槽，为后续原位合成反应提供若干个反应空间；即，为后续纳米氧化亚铜粒子提供生长位置；然后将织物依次浸渍铜源溶液、碱性溶液和还原溶液；然后再将织物置于溶剂中进行反应生成纳米氧化亚铜，反应温度为100℃～300℃，反应时间为5s～1800s；该原位合成过程中，基于在前面的浸轧步骤中控制浸轧后织物的带液率为10％～160％，使得织物上带有溶剂，在高温环境下(100℃～300℃)进行原位合成反应时，织物上的溶剂在原位合成的溶剂中气化，产生瞬时高压，几秒内即可完成纳米氧化亚铜的合成，降温时，得到的纳米氧化亚铜颗粒固定在前处理形成在纤维表面的凹槽中，显著提高了纳米氧化亚铜颗粒与织物的结合牢度，保证了织物的长效抗菌抗病毒性能，且制备方法操作简单，使用范围广，降低了生产成本，具有较高的应用价值。In summary, the preparation method of the antibacterial and antiviral protective material provided by the present invention comprises the following steps: performing a micro-dissolution pretreatment on the fabric by selecting a suitable pretreatment solution, so that grooves are formed on the fiber surface, providing a plurality of reaction spaces for the subsequent in-situ synthesis reaction; that is, providing a growth position for the subsequent nano cuprous oxide particles; then the fabric is sequentially immersed in a copper source solution, an alkaline solution and a reducing solution; and then the fabric is placed in a solvent for reaction to generate nano cuprous oxide, the reaction temperature is 100° C. to 300° C., and the reaction time is 5s to 1800s; in the in-situ synthesis process, based on controlling the padding in the previous padding step The liquid carrying rate of the fabric is 10% to 160%, so that the fabric is stained with solvent. When the in-situ synthesis reaction is carried out under a high temperature environment (100°C to 300°C), the solvent on the fabric is vaporized in the in-situ synthesized solvent to generate instantaneous high pressure, and the synthesis of nano cuprous oxide can be completed within a few seconds. When the temperature is lowered, the obtained nano cuprous oxide particles are fixed in the grooves formed on the fiber surface in the pretreatment, which significantly improves the bonding strength between the nano cuprous oxide particles and the fabric, and ensures the long-term antibacterial and antiviral performance of the fabric. The preparation method is simple to operate, has a wide range of applications, reduces production costs, and has high application value.
该抗菌抗病毒防护材料可用于口罩、防护服、面罩、空气净化方面等抗菌材料领域。The antibacterial and antiviral protective material can be used in antibacterial material fields such as masks, protective clothing, face masks, and air purification.
以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围。The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention.
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| CN110205797B (en) * | 2019-06-17 | 2021-09-03 | 常州大学 | Preparation method of cuprous oxide antibacterial textile |
| CN110387738A (en) * | 2019-08-03 | 2019-10-29 | 江苏工程职业技术学院 | A kind of preparation method of visible light-responded graphene-cuprous oxide photocatalytic functional fabric |
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