CN116043539A - 一种纺织品用耐久性抗菌抗病毒剂及其制备方法和应用 - Google Patents
一种纺织品用耐久性抗菌抗病毒剂及其制备方法和应用 Download PDFInfo
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- CN116043539A CN116043539A CN202211606261.9A CN202211606261A CN116043539A CN 116043539 A CN116043539 A CN 116043539A CN 202211606261 A CN202211606261 A CN 202211606261A CN 116043539 A CN116043539 A CN 116043539A
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- 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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- 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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及微生物防护技术领域,尤其涉及IPC D06M13领域,进一步的,涉及一种纺织品用耐久性抗菌抗病毒剂及其制备方法和应用。按质量份计,包括以下原料:40~80份有机抗菌剂、30~60份无机纳米粒子、1~10份交联剂、1~5份硅烷偶联剂、50~80份去离子水、30~60份溶剂。本发明采用硅烷偶联剂对无机纳米粒子进行表面处理,改性的无机纳米粒子与季铵盐和胍盐在化学键合的作用下更好的相结合,进而提高抗菌抗病毒剂的抗菌抗病毒效果;选择不同形状、不同粒径的无机纳米粒子,在交联剂的作用下,使抗菌抗病毒有效成分与纤维分子结合的更加牢固,有效避免和减缓了抗菌抗病毒有效成分从纺织品表面脱离。
Description
技术领域
本发明涉及微生物防护技术领域,尤其涉及IPC D06M13领域,进一步的,涉及一种纺织品用耐久性抗菌抗病毒剂及其制备方法和应用。
背景技术
棉、麻、丝等天然纺织品和各种化纤纺织品与人们的日常生活息息相关,但也是细菌、真菌等微生物喜好的生存之地。随着生活质量的提高,人们对服装、卫生用品、日用品等耐用消费品的卫生安全性有了较高的要求。纺织品可以为微生物的生长提供碳源和氮源,且纺织品在使用过程中容易沾附汗水,皮脂等排泄物,而这些物质又是微生物生长繁殖的良好营养物质;同时,由于人体的温度适宜细菌的生长,若织物上带有病原性细菌,这些细菌就容易大量繁殖并在适宜条件下侵入人体从而引起疾病。宾馆、洗浴中心等公共场所用毛巾、被单等,出入公共场所时人们穿戴的衣物等,特别的,医疗、医药、及食品等行业所使用的纺织品辅料(纱布、手术巾)、床单、工作服等均有可能成为有害微生物的传播媒介,造成交叉感染或微生物污染,从而降低医疗、保健及食品等行业的卫生水平。
功能性抗菌纺织品,是一种能够有效抑制或杀灭微生物,如细菌、真菌等且具有卫生保健功能的新型纺织材料,不仅可有效防止疾病的传播和感染,也可极大地降低公共环境的交叉感染风险。目前,纺织品用抗菌抗病毒材料大致包括天然抗菌抗病毒材料、有机合成抗菌抗病毒材料、无机抗菌抗病毒材料。天然抗菌抗病毒材料由于存在弹性、抗皱性、耐磨性差的缺点,其应用受到限制,同时,天然类物质提取繁琐,持久性效果欠佳;有机合成材料尽管抗菌效率高,具广谱抗菌效果,但其耐温性不理想,难以适应纺丝等高温工艺,且具一定毒性,容易产生耐药性;无机材料存在与基材键合不牢固,容易脱落,导致服用性差,功能难以持久等问题。
目前市场上通常使用抗菌抗病毒剂对纺织品进行整理,利用含有抗菌抗病毒组分的乳液、涂料或者树脂,通过浸渍、浸轧或涂覆等手段对纺织品进行处理,再经高温烘焙或其它手段,使有效组分固定在纤维或织物上。
中国专利CN 109295711 B公开了一种耐水洗型抗病毒抗菌纤维的制备方法及纤维制品,其中方法包括:将原料纤维或纤维织物的原料在前处理工作溶液中进行煮漂亲水性处理;制备由N羟甲基酰胺类交联剂、异噻唑啉酮类化合物和吡卜酰胺结构的氯苯咪唑类高分子化合物组成的抗病毒抗菌接枝液;将亲水性处理后的纤维或纤维织物浸渍于含有抗病毒抗菌基团的抗病毒抗菌接枝液中充分润湿,通过接枝改性和化学修饰反应得到具有抗病毒抗菌功能的纤维;将具有抗病毒抗菌功能的纤维或纤维织物进行焙烘定性。可见该技术方案的抗菌抗病毒接枝液的有效成分属于有机类抗菌抗病毒材料,在一定的温度条件下容易分解从而导致抗菌、抗病毒功能失效。
发明内容
本发明的目的是将有机材料和无机材料结合起来,制备复合型抗菌抗病毒材料,充分发挥不同组分之间的共同作用,实现抗菌抗病毒的高效性和全面性,功能性和舒适性的协调统一。
本发明的第一方面提供了一种纺织品用耐久性抗菌抗病毒剂,其特征在于,按质量份计,包括以下原料:40~80份有机抗菌剂、30~60份无机纳米粒子、1~10份交联剂、1~5份硅烷偶联剂、50~80份去离子水、30~60份溶剂。
在一些优选的实施方式中,所述有机抗菌剂选自季铵盐类、吡啶类、季膦盐类、有机锡类、异噻唑啉酮类、卤代胺类、胍盐类中的一种或多种组合。
优选的,所述有机抗菌剂为季铵盐和胍盐的组合。
优选的,所述季铵盐和胍盐的质量比为(1~3):(1~3)。
在一些优选的实施方式中,所述季铵盐选自十二烷基二甲基氯化铵、十二烷基二甲基苄基氯化铵、十六烷基三甲基氯化铵、十六烷基二甲基氯化铵、十八烷基二甲基氯化铵、十八烷基甲基苄基氯化铵、十八烷基三甲基氯化铵、十八烷基二甲基苄基氯化铵中的一种或多种组合。
优选的,所述季铵盐选自十二烷基二甲基苄基氯化铵和十八烷基二甲基氯化铵的组合。
优选的,所述十二烷基二甲基苄基氯化铵和十八烷基二甲基氯化铵的质量比为(1~3):(1~3)。
在一些优选的实施方式中,所述胍盐选自聚六亚甲基单胍盐酸盐、聚六亚甲基双胍盐酸盐、聚六亚甲基双胍月桂酸盐、聚六亚甲基双胍乙酸盐、聚六亚甲基双胍丙酸盐中的一种或多种组合。
优选的,所述胍盐为聚六亚甲基双胍盐酸盐。
在一些优选的实施方式中,所述无机纳米粒子选自纳米银、纳米二氧化硅、纳米氧化铜、纳米二氧化钛、纳米氧化锌、纳米氧化银、纳米氧化铝中的一种或多种组合。
优选的,所述无机纳米粒子选自纳米银、纳米氧化锌和纳米二氧化钛的组合。
优选的,所述纳米银、纳米氧化锌和纳米二氧化钛的质量比为(1~4):(1~3):(2~4)。
优选的,所述纳米银为银纳米线。
优选的,所述银纳米线的直径为20~40nm。
优选的,所述纳米氧化锌的粒径为100~300nm。
优选的,所述纳米二氧化钛为金红石型二氧化钛纳米棒。
优选的,所述金红石型二氧化钛纳米棒的粒径为20~50nm。
在一些优选的实施方式中,所述交联剂选自水性聚氨酯类交联剂、异氰酸酯、多功能聚碳化二亚胺、1,3-二氨基丙烷、丁烷四羧酸、聚丙烯酸酯类交联剂、二乙烯基苯、双丙酮丙烯酰胺、柠檬酸、2-磷酸基-1,2,4-三羧酸丁烷中的一种或多种组合。
在一些优选的实施方式中,所述硅烷偶联剂选自γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷中的任意一种。
在一些优选的实施方式中,所述溶剂为水和乙醇的混合物。
优选的,所述水和乙醇的体积比为1:1。
本发明中,先采用硅烷偶联剂对无机纳米粒子进行表面处理,硅烷偶联剂的水解产物上的羟基和无机纳米粒子表面的羟基发生化学反应,从而接枝在无机纳米粒子表面,经硅烷偶联剂改性的无机纳米粒子与季铵盐和胍盐能通过化学键合的作用更好的相结合,通过无机纳米粒子和有机抗菌剂的共同作用,进而提高纺织品用抗菌抗病毒剂的抗菌抗病毒作用。尤其当选择纳米银、纳米氧化锌和纳米二氧化钛作为无机纳米粒子,纳米银为银纳米线,银纳米线的直径为20~40nm,纳米氧化锌的粒径为100~300nm,纳米二氧化钛为金红石型二氧化钛纳米棒,金红石型二氧化钛纳米棒的粒径为20~50nm时,还可以提高纺织品用抗菌抗病毒的耐水洗性。本申请人猜测:通过选择不同形状、不同粒径的无机纳米粒子,使得季铵盐和胍盐分子链能与硅烷偶联剂改性后的无机纳米粒子更加充分的缠绕掺杂,使无机纳米粒子与有机抗菌剂复合程度更高,在交联剂的作用下,使抗菌抗病毒有效成分与纤维分子结合的更加牢固,从而有效避免和减缓了抗菌抗病毒有效成分的从纺织品表面脱离。
本发明另一方面提供了一种纺织品用耐久性抗菌抗病毒剂的制备方法,包括以下步骤:按质量份,将硅烷偶联剂溶于溶剂中,加入无机纳米粒子,搅拌均匀后加入有机抗菌剂,再次搅拌均匀后加入交联剂和去离子水即得。
本发明还提供了一种纺织品用耐久性抗菌抗病毒剂的应用,用于制备抗菌抗病毒纺织品。
有益效果:本发明中,先采用硅烷偶联剂对无机纳米粒子进行表面处理,硅烷偶联剂的水解产物上的羟基和无机纳米粒子表面的羟基发生化学反应,从而接枝在无机纳米粒子表面,经硅烷偶联剂改性的无机纳米粒子与季铵盐和胍盐能通过化学键合的作用更好的相结合,通过无机纳米粒子和有机抗菌剂的共同作用,进而提高纺织品用抗菌抗病毒剂的抗菌抗病毒作用;通过选择不同形状、不同粒径的无机纳米粒子使得季铵盐和胍盐分子链能与硅烷偶联剂改性后的无机纳米粒子更加充分的缠绕掺杂,使无机纳米粒子与有机抗菌剂复合程度更高,在交联剂的作用下,使抗菌抗病毒有效成分与纤维分子结合的更加牢固,从而有效避免和减缓了抗菌抗病毒有效成分的从纺织品表面脱离。
具体实施方式
实施例1
实施例1提供了一种纺织品用耐久性抗菌抗病毒剂,其特征在于,按质量份计,包括以下原料:70份有机抗菌剂、50份无机纳米粒子、6份交联剂、3份硅烷偶联剂、70份去离子水、50份溶剂。
所述有机抗菌剂为季铵盐和胍盐的组合。
所述季铵盐和胍盐的质量比为1:1。
所述季铵盐选自十二烷基二甲基苄基氯化铵(CAS号:8001-54-5)和十八烷基二甲基氯化铵(CAS号:122-19-0)的组合。
所述十二烷基二甲基苄基氯化铵和十八烷基二甲基氯化铵的质量比为1:2。
所述胍盐为聚六亚甲基双胍盐酸盐(CAS号:32289-58-0)。
所述无机纳米粒子选自纳米银、纳米氧化锌和纳米二氧化钛的组合。
所述纳米银、纳米氧化锌和纳米二氧化钛的质量比为2:3:3。
所述纳米银为银纳米线。
所述银纳米线的直径为30nm,购买自江苏先丰纳米材料科技有限公司,型号:102883。
所述纳米氧化锌的粒径为150nm,购买自博华斯纳米科技有限公司,型号Brofos-ZnO-150。
所述纳米二氧化钛为金红石型二氧化钛纳米棒。
所述金红石型二氧化钛纳米棒的粒径为50nm,购买自博华斯纳米科技有限公司,型号:Brofos-TiO2-N50。
所述交联剂为丁烷四羧酸(CAS号:1703-58-8)。
所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷(CAS号:919-30-2)。
所述溶剂为水和乙醇的混合物。
所述水和乙醇的体积比为1:1。
一种纺织品用耐久性抗菌抗病毒剂的制备方法,包括以下步骤:按质量份,将硅烷偶联剂溶于溶剂中,加入无机纳米粒子,搅拌均匀后加入有机抗菌剂,再次搅拌均匀后加入交联剂和去离子水即得。
实施例2
实施例2提供了一种纺织品用耐久性抗菌抗病毒剂,其具体实施方式同实施例1,不同点在于,按质量份计,包括以下原料:60份有机抗菌剂、60份无机纳米粒子、6份交联剂、4份硅烷偶联剂、80份去离子水、60份溶剂。
实施例3
实施例3提供了一种纺织品用耐久性抗菌抗病毒剂,其具体实施方式同实施例1,不同点在于,纳米银为纳米银粉,购买自江苏先丰纳米材料科技有限公司,型号:100422。
实施例4
实施例4提供了一种纺织品用耐久性抗菌抗病毒剂,其具体实施方式同实施例1,不同点在于,所述无机纳米粒子为纳米银和纳米氧化锌的组合,纳米银和纳米氧化锌的质量比为2:3。
性能测试:
将实施例1~4制备的抗菌抗病毒剂用去离子水稀释20倍,制得纺织品整理液。
将涤棉混纺织物以浴比1∶10分别浸渍在以上实施例1~4所制备的纺织品整理液中,浸渍温度为60℃,浸渍时间为3min,然后将浸渍后的涤棉混纺织物进行脱水、烘焙处理,烘焙温度为150℃,烘焙时间为40s,分别得到样品1~4。
对样品1~4进行如下性能测试,结果记录在表1:
以下样品洗涤参照FZ/T 73023-2006,附录C中规定的方法进行洗涤。
1、抗菌性能:参照GB/T20944.3标准。
2、抗病毒性能:参照ISO 18184-2019标准。
3、安全性能:参照FZ/T73023-2006,附录C进行一次标准洗涤后,参照GB/T31713-2015,附录A,检测抗菌物质溶出性。
测试结果:
表1:
Claims (10)
1.一种纺织品用耐久性抗菌抗病毒剂,其特征在于,按质量份计,包括以下原料:40~80份有机抗菌剂、30~60份无机纳米粒子、1~10份交联剂、1~5份硅烷偶联剂、50~80份去离子水、30~60份溶剂。
2.根据权利要求1所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述有机抗菌剂选自季铵盐类、吡啶类、季膦盐类、有机锡类、异噻唑啉酮类、卤代胺类、胍盐类中的一种或多种组合。
3.根据权利要求2所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述季铵盐选自十二烷基二甲基氯化铵、十二烷基二甲基苄基氯化铵、十六烷基三甲基氯化铵、十六烷基二甲基氯化铵、十八烷基二甲基氯化铵、十八烷基甲基苄基氯化铵、十八烷基三甲基氯化铵、十八烷基二甲基苄基氯化铵中的一种或多种组合。
4.根据权利要求2所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述胍盐选自聚六亚甲基单胍盐酸盐、聚六亚甲基双胍盐酸盐、聚六亚甲基双胍月桂酸盐、聚六亚甲基双胍乙酸盐、聚六亚甲基胍磷酸盐、聚六亚甲基双胍丙酸盐中的一种或多种组合。
5.根据权利要求2所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述季铵盐和胍盐的质量比为(1~3):(1~3)。
6.根据权利要求1所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述无机纳米粒子选自纳米银、纳米二氧化硅、纳米氧化铜、纳米二氧化钛、纳米氧化锌、纳米氧化银、纳米氧化铝中的一种或多种组合。
7.根据权利要求6所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述纳米银、纳米氧化锌和纳米二氧化钛的质量比为(1~4):(1~3):(2~4)。
8.根据权利要求1所述的一种纺织品用耐久性抗菌抗病毒剂,其特征在于,所述交联剂选自水性聚氨酯类交联剂、异氰酸酯、多功能聚碳化二亚胺、1,3-二氨基丙烷、丁烷四羧酸、聚丙烯酸酯类交联剂、二乙烯基苯、双丙酮丙烯酰胺、柠檬酸、2-磷酸基-1,2,4-三羧酸丁烷中的一种或多种组合。
9.一种根据权利要求1~8任一项所述的纺织品用耐久性抗菌抗病毒剂的制备方法,其特征在于,包括以下步骤:按质量份,将硅烷偶联剂溶于溶剂中,加入无机纳米粒子,搅拌均匀后加入有机抗菌剂,再次搅拌均匀后加入交联剂和去离子水即得。
10.一种根据权利要求1~8任一项所述的纺织品用耐久性抗菌抗病毒剂的应用,其特征在于,用于制备抗菌抗病毒纺织品。
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