CN1237087A - 耐久的、可再生的杀微生物织物 - Google Patents
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Abstract
本发明提供了,尤其是耐久、可再生的杀微生物织物,以及制备所述织物的方法。这种织物可方便地使用一种湿法整理法将杂环的N-卤代胺(halamine)以共价键的形式接到纤维素基材料或其它聚合物材料上而制备得到。制备出的本发明织物对致病的微生物具有广谱杀生物活性。而且,这种织物的杀生物活性可用卤化的溶液洗涤后再生。
Description
在纺织工业中重要的且正发展的部分是药物和有关健康和卫生保键方面的内容。在涉及药物应用中所使用的织物材料包括,例如,外科用的罩袍、帽子和口罩、病人用的布帘、绷带、抹布以及各种大小的盖布。但是,这种织物会带来交叉感染并会传播由微生物引起的疾病。这样,由致命的HIV病毒、隐伏的肝炎病毒或其它传染病传播引起的感染越来越关注药物/健康关护/卫生保健部门使用的防护设施和工作人员的制服。目前,医药应用中使用的织物材料都是一次性的无纺合成织品,它们既不具有杀菌性,也不是可再使用的。这种织物织品通过阻断微生物的传播,而不是通过抑制这些微生物生长而提供了保护。因此,与污染的织物织品表面接触而带来的交叉感染还是有问题。结果为了预防疾病的交叉感染和传播,必须在使用后对污染的材料进行合适地灭菌然后扔掉。但不幸的是这种灭菌和抛弃过程使健康关护中的成本升高并且使它们产生更多的有毒生物废料。
因此,理想的是减少或完全消除接触污染织物而带来的细菌感染,并且还希望通过抑制织品上的微生物的生长而预防人与人在穿着或使用污染织物过程中而带来的致病细菌的传播。而且,还希望外科医生的外套、医院的毯罩和铺床材料、内衣、袜子和制服是杀菌的,以使能提供可能的、最好的保护作用。另外,还希望在,尤其是,宾馆用毛巾、床上用品、袜子以及其它卫生用品中使用有杀菌作用的织物。
目前,通常对能提供保护作用的医护/健康关护/卫生人员的技术有两种分类法。(1)物理技术,它能通过选择不渗透的或多微孔的包括抗菌剂的织品构造和涂层来形成物理屏障,以防止微生物渗透或传播;(2)化学技术,它通过接枝或其它化学技术而将活性功能剂经入到织品或纤维上。一次性材料属于第一分类中的实例。涂覆法涉及将不透的材料施用到织品的表面,因此而阻断微生物的渗透和穿透。但是疾病的交叉感染和扩散仍会通过接触涂层表面而产生,因此会对处理污染材料的工作人员产生潜在的威胁。进一步地讲,不透性会使穿戴者不舒服,进而会使功效降低。
因此,通过化学方法而将抗菌剂连接到材料的表面上或其整体中使得抗菌性能在耐久性和功效上更实用。通过化学方法达到耐久的抗菌效果有两种主要方式。一种方式是通过与已加工的织品接触而缓慢释放杀菌剂。在该方法(世界范围内广泛采用的方法)中,通过化学或物理方法将足量的化学剂浸渍到纤维上。然后杀菌剂会从已加工的织品上缓慢地释放入介质中,借此可与微生物接触并抑制它们的生长。不幸的是,这种化学试剂如果不是通过共价键浸入到织品的表面上,它们就会很容易地被洗掉。而且其抗菌功能也不会再生。
在第二种方法中,使用了一种更富有革新性的技术,其中用杀菌化合物或有可能成为杀菌化合物的化合物对织物材料进行化学改性,其中这种化合物的抗菌性能会在简单的清洗后再生。这些潜在的抗菌基团会在用某种普通的化学品清洗后而具有杀菌性,这种化学品如稀释的漂白液。大约在35年以前,Gagliardi等人第一次提出了抗菌处理再生的理论,希望使用某些特定的溶液清洗使用过的织品而使其丧失的功能再生(参见Am.Dyest.Reptr.,51,49(1962))。但是虽然进行过各种努力,但并未得到任何商业产品。
从上述的角度看来,本领域对耐久的和可再生的杀微生物织物存在需求。本发明通过提供,尤其是,耐久的和可再生的杀微生物织物而满足了这种需要。
本发明提供了,尤其是,耐久的和可再生的杀微生物织物及其制备方法。这种织物可使用一种经典的湿法整理法以将杂环的N-卤代胺(halamine)以共价键的形式附着到纤维素基材料或其它聚合物材料上而制得。一旦制成,本发明的织物就会对致病的微生物具有广谱杀菌活性。而且,这种织物的杀菌活性还会在用卤化溶液清洗后再生。
在一个实施方案中,本发明提供了一种制备杀微生物纤维素、纤维素/聚酯或聚酯织物前体的方法,该方法包括:(a)将一种纤维素、纤维素/聚酯或聚酯织物浸在水性处理溶液中,所述溶液包括一种杂环的N-卤代胺、一种润湿剂和一种催化剂;(b)从纤维素、纤维素/聚酯或聚酯织物中除去过量的处理液;(c)干燥该纤维素、纤维素/聚酯或聚酯织物;(d)将干燥后的纤维素、纤维素/聚酯或聚酯织物固化;(e)清洗该固化的纤维素、纤维素/聚酯或聚酯织物以除去过量的试剂;和(f)将处理后的纤维素、纤维素/聚酯或聚酯织物干燥以除去水。
在另一实施方案中,本发明提供了一种使纤维素、纤维素/聚酯或聚酯织物具有杀菌性的方法,该方法包括:(a)用卤化溶液清洗杀微生物的纤维素、纤维素/聚酯或聚酯织物前体,该杀菌织物前体是根据上述方法制备的;和(b)将该处理后的杀菌纤维素、纤维素/聚酯或聚酯织物干燥以除去水。在该方法中,卤化溶液可以是氯溶液或者溴溶液。在一目前优选的实施方案中,该卤化溶液是氯溶液(例如氯漂白溶液如Clorox)。用卤化溶液对杀微生物纤维素、纤维素/聚酯或聚酯织物前体进行清洗使得该织物具有杀生物性,另外它还对该织物进行了灭菌。
在又一实施方案中,本发明提供了用于整理织品的组合物,即一种水性处理液,该组合物包括一种润湿剂;和杂环的N-卤代胺。在一优选的实施方案中,该组合物还包括一种催化剂。在进一步优选的实施方案中,该组合物还包括添加剂(例如软化剂和防水剂)用来使组合物具有受欢迎的特征。
本发明的杀微生物织物的应用领域非常广泛。例如,该杀微生物织物材料能给医务领域以及相关的健康关护和卫生保健领域的工作人员提供杀菌防护布。与现有所使用的织物相比,本发明的织物不是用来作为微生物的屏障,而是对它们进行消毒。因此,这种可再生的重复使用的杀菌材料能够替代目前所使用的医务织物-一次性的无纺织品,借此可大大降低医院的维持费用和废弃品的消耗。本发明织物的杀微生物特性能有利地用作女性衣物、内衣、袜子以及用于其它卫生保健目的。另外,该杀微生物特性还能赋予毯毡材料以生产一种无味、无菌毯毡。而且,所有的无菌环境,如生物技术和药物工业,都会因使用本发明的杀微生物织物防止来自空气、液体或固体介质的任何污染而受益。
本发明的其它特征、目的和优点及其优选的技术方案都可以通过下文的详细叙述而清楚地呈现出来。
图1演示了本发明中所适用的杂环N-卤代胺的实施例。
图2演示了实例性的杂环N-卤代胺共价地接合到纤维素上的反应路线。
在一个实施方案中,本发明提供了杀微生物纤维素、纤维素/聚酯或聚酯织物前体的制备方法,该方法包括:(a)将纤维素、纤维素/聚酯或聚酯织物浸在一种包括杂环N-卤代胺、润湿剂和催化剂的水性处理溶液中;(b)从纤维素、纤维素/聚酯或聚酯织物中除去过量的处理溶液;(c)干燥该纤维素、纤维素/聚酯或聚酯织物;(d)将干燥后的纤维素、纤维素/聚酯或聚酯织物固化;(e)清洗该固化的纤维素、纤维素/聚酯或聚酯织物以除去过量的试剂;和(f)干燥该处理后的纤维素、纤维素/聚酯或聚酯织物以除去水。
此处所用的“杂环N-卤代胺”是指4-至7-元环,其中环中至少三节是碳,环中有1-3个氮杂原子,还有0-1个氧杂原子,其中0-2个碳节包括一个羰基,且其中至少有1-3个氮原子是被羟烷基(如-CH2OH)或烷氧基烷基(如-CH2OCH3)取代的。另外,该环节上还可以进一步地被烷基(如甲基、乙基等)取代。杂环N-卤代胺被一般性地公开在1996年2月13日授予Worley等人的U.S专利5,490,983中,其被引入本文中作为参考文献。
适用于本发明中的杂环N-卤代胺包括下列,但不限于这些:单羟甲基-5,5-二甲基乙内酰脲(MDMH);1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH);2,2,5,5-四甲基-1,3-咪唑啉-4-酮、6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5,-四甲基-1,3-咪唑啉-2-酮、氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物;和2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单甲氧基化和双甲氧基化衍生物。单甲氧化和双甲氧化化合物的实例分别是单甲氧基甲基-5,5-二甲基乙内酰脲和1,3-二甲氧基甲基-5,5二甲基乙内酰脲。在一目前优选的实施方案中,单羟甲基-5,5-二甲基乙内酰脲和1,3-二羟甲基-5,5-二甲基乙内酰脲是所使用的杂环N-卤代胺。
本发明所用的杂环N-卤代胺可从不同来源购得。例如,单羟甲基-5,5-二甲基乙内酰脲(MDMH)和1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH)可从LONZA、INC、(Fair Lawn,NJ)分别以商品名DANTOLN和GLYDANTXL-1000购得。而且氰尿酸可购自ALDRICH(Milwaukee,WI)。另外,本领域普通技术人员将会很容易地认识到本发明中使用的杂环N-卤代胺可采用传统的合成化学技术以各种方式合成得到。在此方面,本领域普通技术人员会很容易地理解到二甲氧化的衍生物是由二甲基化的衍生物得到的,而单甲氧化的衍生物可以从单-或双甲基化的衍生物得到。
本发明中适用的杂环N-卤代胺的实例显示在图1中。应注意的是这类杂环N-卤代胺的许多广泛用于化妆产品中,其卤化衍生物是,例如,游泳池中使用的主要消毒剂。因此,这些化合物无论是整理后的织品还是在整理过程中将不会对人和环境产生毒害效应。
本发明中所用的“杀微生物的”是指至少杀死某些类别的微生物或者是抑制某些类的微生物生长或繁殖的能力。根据本发明制备的织物对广泛的致命微生物具有杀菌活性。例如,这种织物对具有代表性的革兰氏阳性菌(如金黄色葡萄球菌)和革兰氏阴性菌(如大肠杆菌)具有杀微生物活性。而且,非常重要的是这种织物的杀微生物活性是很容易再生的。
在上述方法的步骤(a)中,水性处理溶液(或可供选择的整理溶液或浴)包括上述的杂环N-卤代胺,润湿剂和催化剂。此处所用的“润湿剂”是指一种物质,它能提供液体铺展表面的速度,即,它使得表面对液体不相斥。合适的润湿剂的实例包括,但并不限于,Triton X-100(Sigma Chemical Co.,St.Louis,MO),SEQUAWET(Sequa Chemical Inc.,Chester,SC)和AMWET(Americal Emulsions Co.,Dalton,GA)。其它适用于本发明中的润湿剂对本领域普通技术人员而言将是已知和常用的。此处所用的“催化剂”是指加速化学反应速度,而本身不被消耗的物质。本发明中适用的催化剂包括下列,但不限于这些:镁盐、锌盐和铵盐。在一目前优选的实施方案中,所使用的催化剂是下列中的一种:MgCl2、Mg(NO3)2、Zn(NO3)2或NH4NO3。
本领域的普通技术人员还将很容易地认识到:该水性处理溶液的各种组分的浓度能依据所使用的特定组分和所需的结果在很大范围内变化。通常,杂环N-卤代胺的浓度至少约0.2%。更普遍地,杂环N-卤代胺的存在浓度为约0.2%-20%,更优选浓度为约0.5%-10%,并且进一步地优选约1%-5%。本领域普通技术人员将会很清楚能使用更高浓度的杂环N-卤代胺(例如50%),但是这种高浓度对引入杀微生物活性而言是不需要的。合适的杀微生物活性在使用低为约0.2%的杂环N-卤代胺时即可得到。通常润湿剂的存在浓度为约0.1%-3%,更优选浓度为约0.2%-1%。所用的催化剂的浓度将取决于所用的杂环N-卤代胺的浓度。通常,杂环N-卤代胺和存在的催化剂的比约为10∶1-5∶1。通常水性处理溶液的pH约为2-6,更优选pH2.5-4.5。
本领域的普通技术人员将会很容易地认识到水性处理液中还可以加入其它的添加剂以使纤维素、纤维素/聚酯或聚酯织物具有理想的特性。这种添加剂可包括本领域普通技术人员已知的和使用过的软化剂和防水剂。可添加到水性处理溶液中的软化剂的实施包括,但不限于,MYKON和SEQUASOFT,均可购自Sequa Chemical Inc.(Chester,SC)。可添加到水性处理溶液中的防水剂的实例包括,但不限于,SEQUAPEL(Sequa ChemicalInc.,Chester,SC),SCOTCHGARD(3M,St.Paul,MN)和其它的本领域普通技术所使用的防水整理溶液。
在实施步骤(a)中,所使用的织物可以是粗纱、纱或织品,不论其是否纺纱、针织或编织的,或者可以是无纺片或网。而且,织物可以由纤维素纤维、聚酯纤维或这些纤维共混物制得。另外,也可使用其它具有反应性官能团(例如-OH)的聚合物材料。这种聚合物材料包括,但不限于,聚乙烯醇(PVA),淀粉和蛋白质。在整理或处理浴中润湿该织物时,可使用间歇或连续将粗纱、纱或织品通过水溶液的普通织物设备,其速度为可将织物材料完全和均匀浸湿的任何速度。
在步骤(b)中,通过普通的机械方法如将织物通过挤压辊、离心分离、排水或压轧(padding)除去过量的水性处理溶液。在一优选的实施方案中,通过压轧除去过量的水性处理液。
在步骤(c)中,干燥纤维素、纤维素/聚酯或聚酯织物的温度约为50-90℃且更优选约为75-85℃,持续约3-8分钟,更优选约5分钟。
在步骤(d)中,干燥后的纤维素、纤维素/聚酯或聚酯纤维的固化温度为约120℃-180℃,更优选约140℃-160℃,持续时间约3-8分钟,更优选约5分钟。加热可在烘箱中、优选直接指向织物表面的加压通风,通过一个气口排出烟。
在步骤(e)中,清洗干燥后的纤维素、纤维素/聚酯或聚酯织物。步骤(e)中的处理后的织物可用热或冷水清洗。所形成的共价键相对于洗衣机中或大规模连续或间歇织物清洗设备中的机械搅拌而言是稳定的、不溶性的、持久的。
最后的干燥,步骤(f)可以使用任意普通的方式如机械的布干燥器中烘箱干燥、线式干燥或滚筒干燥。优选干燥温度约为80-120℃,干燥时间少于15分钟。
在另一优选的实施方案中,本发明提供了一种使纤维素、纤维素/聚酯或聚酯织物具有杀微生物性的方法,该方法包括:(a)用一种卤化溶液清洗杀微生物纤维素、纤维素/聚酯或聚酯织物前体,该杀微生物织物前体是根据上述制备的;和(b)干燥处理后的杀微生物纤维素、纤维素/聚酯或聚酯织物以除去水。在该方法中,卤化溶液可以是氯溶液或溴溶液(例如氯漂白溶液如(Clorox)。用卤化溶液清洗杀微生物纤维素、纤维素/聚酯或聚酯织物前体使该织物具有杀微生物性的同时,还能将该织物灭菌。而且如前述所解释的,织物的杀微生物活性,即氧化特性可在有规律地清洗中通过周期性地用卤化溶液进行清洗而再生。
在又一实施方案中,本发明提供了用于整理织品的组合物,该组合物包括一种润湿剂和一种杂环N-卤代胺。在一优选的实施方案中,该组合物还包括一种催化剂。在更优选的实施方案中,该组合物还包括添加剂(例如软化剂和防水剂)以赋予理想的特征。涉及杂环N-卤代胺、润湿剂、催化剂、添加剂及其各种浓度的讨论也充分适用于该组合物,因此在此不再重复这些讨论。水性处理溶液的pH值通常在约pH2-6,优选约pH2.5-4.5。本领域普通技术人员将会很清楚地明白上述组合物可制成浓缩形式或者以适于立即使用的形式,即合适的试剂浓度。
考虑到使用上述方法和组合物制备的整理过的织物的抗菌和机械性能,本领域普通技术人员将会很容易地理解这种整理后的织物可有利地用在制备下列用品中:外科医生的袍罩、帽子、面罩、外科用盖物、病人用帘罩、毯毡,床上材料、内衣、袜子、制服等。本领域普通技术人员将会很容易地理解本发明整理后的织物也能有利地用于其它的各种目的,如宾馆用毛巾、床上用品、卫生用品、各种防护农药和其它有毒化学品等的布上。
通过以下的具体实施例更详细地描述了本发明。下述实施例只用于演示目的,不是用来限制或限定本发明的。
实施例Ⅰ
该实施例例举了用单羟甲基-5,5-二甲基乙内酰脲(MDMH或抗-1)对织物的整理
制备在600ml去离子水中的包含24g单羟甲基-5,5-二甲基乙内酰脲、4.8g氯化镁和0.6gTriton X-100(润湿剂)的整理浴。用1ml的0.1NHCL溶液调整该整理浴的pH到3.4。然后,将140.9g纯棉织品(#400 Testfabrics,Inc.,Middlesex,NJ)和141.4克棉/聚酯(35/65)共混织品(#7409 Testfabrics,Inc.,Middlesex,NJ)浸渍在该浴中超过5分钟,并用吸液率超过80%的浸轧机浸轧。将该织品又浸渍和浸轧一次后,在80℃干燥5分钟。然后将该织品在160℃固化5分钟。最后,将该整理后的织品在低水量、约60℃的温度下用90g美国织物化学家和着色师学会(American Association of TextileChemist and Colorists,AATCC)标准参考浸透剂124机洗30分钟。将该织品干燥后称重,得到42.8g(增加1.35%)的棉织品和142.4g(增加0.71%)的棉/聚酯共混织品。用KBr制片后的棉制品在1718cm-1和1770cm-1显示出突出的红外吸收峰。
此后,用含约0.01%活性氯的稀释的Clorox溶液清洗该整理后的织品。使用实施例Ⅲ中讲述的方法测定该织品抗典型革兰氏阳性菌(如黄色葡萄球菌(ATCC 5368))和革兰氏阴性菌(如大肠杆菌(ATCC 2666)的抗菌性能。
实施例Ⅱ
本实施例例举了用1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH或抗-2)对织品进行的整理
制备在800ml去离子水中包含48g 1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH或抗-2)、9.6g氯化镁和0.8g Triton X-100(润湿剂)的整理浴。用20ml 0.01N HCl溶液调整该整理浴的pH到3.1。然后将144.7g纯棉织品(#400 Testfabrics,Inc.,Middlesex,NJ)和143.2g棉/聚酯(35/65)共混织品(#7409,Testfabrics,Inc.,Middlesex,NJ)浸渍在该浴中超过5分钟,并用吸液率超过80%的浸轧机浸轧。将该织品又浸清和浸轧一次后,在80℃干燥5分钟。然后将该织品在160℃固化5分钟。最后,将该整理后的织品在低水量、约60℃的温度下用90g AATCC标准参考浸透剂124机洗30分钟。将该织品干燥后称重,得到147.9g(增加2.22%)的棉织品和145.5g(增加1.62%)的棉/聚酯共混织品。用KBr制片后的棉制品在1718cm-1和1770cm-1显示具有突出的红外吸收峰。
此后,用含约0.01%活性氯的稀释的Clorox溶液清洗该整理后的织品。使用实施例Ⅲ中讲述的方法测定该织品抗典型革兰氏阳性菌(如金黄色葡萄球菌(ATCC 5368)和革兰氏阴性菌(如大肠肝菌(ATCC 2666))的抗菌性能。
实施例Ⅲ
该实施例例举了使用AATCC测试方法147实施的抗-1整理后的织品的定量抗菌研究。
#405(纯棉,Testfabrics,Inc.,Middlesex,NJ)和#7402(棉/聚酯35/65,Testfabrios,Inc.,Middlesex,NJ)的织品样品以类似于实施例Ⅰ中所述的方式进行整理。在整理棉织品中所用整理剂的浓度是约5-15%,由于棉/聚酯(35/65)共混织品中纤维素的浓度较低,所以其所用的整理剂的浓度约为5-20%。最终的杀菌性能通过用含0.25%氯的稀释Clorox溶液清洗整理后的织品而在每次清洗后引入到该织品上。根据AATCC测试法147进行定量的抗菌测试。
在AATCC测试法147中,将两片尺寸大小为25mm×50mm的氯化织物放置在营养琼脂板上,该板上已用4mm的接种环用稀释的细菌溶液划五道。该稀释的细菌溶液是将1.0ml 24小时肉汤培养液转移到9.0ml的无菌蒸馏水中而制成的。在37℃温育该琼脂板18-24小时。测量沿测试样品的任一侧的划痕的抑制带的最小宽度。表Ⅰ列示了用不同浓度抗-1整理后的织品的定性杀菌评估结果。即使使用5%的整理剂浓度和约1%的试剂增加量,处理后的织品都具有持久、可再生的抗菌性能。表Ⅰ整理后的棉(#405)和棉/聚酯35/65(#7402)的结果
织品 | 抗-1的浓度 | 增加量% | 杀菌结果*清洗20次后大肠杆菌金色萄萄球菌 | 杀菌结果清洗50次后大肠杆菌金色萄萄球菌 | ||
#405 | 5 | 1.2 | >3mm | >1mm | >1mm | ~1mm |
10 | 2.3 | >8mm | >3mm | >3mm | >1mm | |
15 | 3.1 | 全部杀死 | 全部杀死 | >4mm | >4mm | |
#7402 | 5 | 0.8 | >3mm | >1mm | >1mm | ~1mm |
10 | 1.4 | >3mm | >1mm | >2mm | ~1mm | |
15 | 1.6 | 全部杀死 | 全部杀死 | >2mm | >1mm | |
20 | 2.0 | 全部杀死 | >4mm | >3mm | >1mm |
*杀菌结果是用AATCC测试方法147测定的,最小的消毒距离以毫米(mm)测定。洗涤测试是根据AATCC测试法124和AATCC标准参考浸透剂(Detergent)124热机洗进行的。
实施例Ⅳ
用实施例Ⅰ中讲述的方法用功能剂(functional agent)对四种衣物材料,即#400、#4702(35/65棉/聚酯)、Terry布和Rayon(均来自Testfabrics,Inc.,Middlesex,NJ)进行化学整理。用抗-1整理后的不同织品的抗菌结果列于表Ⅱ中。功能剂在该织品上的增加百分比仅约为1%。但是通过稀释的Clorox洗涤该织品而使该织品的杀菌性能活化后,细菌抑制带相对增大的。该结果显示能容易地向含纤维素的材料中引入功能整理剂,得到所需的抗广谱微生物的功能。如果需要彻底的消毒,可提高整理剂的浓度以提高该整理剂的增加量,如以上讨论的那样。但是,在大多数应用中,只需要适宜的杀菌性能,特别是在抗气味整理中。表Ⅱ用抗-1整理后的不同织品的抗菌结果
织品 | 整理剂的增加量% | 活化后抗金色葡萄球菌的杀菌结果(mm) | 活化后抗大肠杆菌的杀菌结果(mm) |
棉布#400 | 1.43 | >1.0 | >2.0 |
人造纤维 | 1.21 | >1.0 | >1.0 |
的确良/棉#7402 | 1.19 | >4.0 | >10 |
Terry布100%棉 | 1.40 | 全部杀死 | >10 |
对照棉布#400 | / | 全部生长 | 全部生长 |
实施例Ⅴ
本实施例例举了抗-1整理后的织品的定量抗菌研究(AATCC TestMethod 100)。
抗-1整理后的织品的杀菌性能的定量研究显示即使使用非常低浓度的整理浴,也能在织品上得到杀菌性能。在这个研究中采用了AATCC测试法100。根据这个测试方法,四片刮软的环状织物样本4.8±0.1(约lg)接种了在250ml罐中的1.0±0.1ml接种物。该接种物是一种营养肉汤培养物,其含有多于1.0×106菌落形成单位(CFU)的有机体。将该样本接种后,将它们用在罐中的100ml的0.02%的硫代硫酸钠溶液中和。接触时间就是接种到中和的时间。剧烈振荡该罐子,连续稀释该中和溶液。将稀释液,通常为100、101和102置于营养琼脂上,37℃温育18-24小时。计算接种后的经整理织品上复活的细菌数,并将之与未处理织品上的进行比较。六log减少是指细菌的总失活,1log的减少是指整理后的织品将细菌量从106CFU减少到105CFU。对按照实施例Ⅰ中的方法用吸液率低于1%的从含1%-6%单羟甲基-5,5-二甲基乙内酰胺溶液制备的整理后的织品进行了测试。这种织品的杀菌性能示于表Ⅲ中。表Ⅲ抗-1的整理浓度对细菌减少速度的影响
#400是100%棉平纹纺织织品,#7402是65/35聚酯/棉的平纹纺织织品。6log减少是指杀灭全部细菌。
抗-1剂的浓度 | 材料 | 吸取量% | 接触时间内的细菌减少量0分钟 30分钟 60分钟 | |||||
大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | |||
1% | #400 | 0.65 | 无 | 无 | 无 | 1log | 无 | 无 |
#7402 | 0.14 | 无 | 无 | 1log | 无 | 1log | 无 | |
2% | #400 | 0.03 | 无 | 1log | 6log | 6log | 6log | 6log |
#7402 | 0.07 | 无 | 无 | 6log | 1log | 6log | 6log | |
4% | #400 | 0.47 | 6log | 6log | 6log | 6log | 6log | 6log |
#7402 | 0.45 | 6log | 6log | 6log | 6log | 6log | 6log | |
6% | #400 | 0.70 | 6log | 6log | 6log | 6log | 6log | 6log |
#7402 | 0.70 | 6log | 6log | 6log | 6log | 6log | 6log |
表Ⅳ显示了氯浓度对用实施例1中方法整理后的抗菌织物的杀菌性能的影响。每次用不同浓度的氯再生循环后会损失少量的接枝杂环。选择浓度为4%的单羟甲基-5,5-二甲基乙内酰脲作为整理浴,抗-1的吸收率为1.29%。结果显示#7402织品具有某些意想不到的效果,其比棉织品具有更持久的杀菌性能。优选用较低的氯浓度进行杀菌性能的再生。表Ⅳ氯浓度对杀菌性能的影响(细菌减少速度)
#400是100%的棉,#7409是65/35聚酯/棉混纺物,接触时间=60分钟。6log减少是指杀灭全部细菌。0log减少是指对细菌生长有某种减少,延长接触时间会进一步减少。洗涤测试是按照AATCC-124使用90g AATCC浸透剂124机器热(140℃)洗15分钟进行的。
Cl% | 织品 | 洗涤五次后 | 洗涤10次后 | 洗涤15次后 | 洗涤20次后 | ||||
大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | ||
0.01 | #400 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log |
#7409 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | |
0.1 | #400 | 6log | 6log | 6log | 6log | 6log | 6log | 1log | 0log |
#7409 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | |
0.25 | #400 | 6log | 6log | 2log | 0log | 1log | 0log | 1log | 0log |
#7409 | 6log | 6log | 6log | 6log | 6log | 6log | 1log | 1log |
实施例Ⅵ
本实施例例举了抗-2整理后的织品的定量抗菌研究(AATCC测试法100)。
用抗-2,即1,3-二羟甲基-5,5-二甲基乙内酰脲按照实施例Ⅱ中的方法整理后的织品用AATCC测试方法100(在实施例Ⅳ中有简要叙述)进行了测试。在该测试中,用含0.01%活性氯的稀释Clorox溶液使整理后的织品氯化。抗-2整理后的织品的杀菌性能列于表Ⅴ中。表Ⅴ抗-2整理后的织品的持久抗菌性
#400是100%的棉,#7409是65/35聚酯/棉混纺物。接触时间60分钟。6log减少是指杀灭全部细菌。0log是指对细菌生长有某种减少,延长接触时间会进一步减少。洗涤测试是按照AATCC-124法使用90gAATCC浸透剂124机器热洗(140℃)15分钟进行的。
抗-2的浓度 | 织物 | 洗涤5次后 | 洗涤10次后 | 洗涤15次后 | 洗涤20次后 | 洗涤20次后 | |||||
大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | 大肠杆菌 | 金色葡萄球菌 | ||
2% | #400 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log |
#7409 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | |
6% | #400 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log |
#7409 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | |
10% | #400 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log |
#7409 | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log | 6log |
实施例Ⅶ
本实施例例举了抗-2整理后的持久的压制性能(press properties)
根据实施例Ⅱ中讲述的方法用抗-2整理后的织品也具有持久的压制性能,这是可理解的,因为DMDMH的结构非常类似于1,3-二羟甲基-4,5-二羟基亚乙基脲(DMDHEU)。持久的压制性能是根据AATCC测试法66进行测试的。在该测试中,大小为15×40mm的#400棉织的六个经向样本和六个纬向样本在调节室(21±l℃,相对湿度65±2%)中调节24小时以上。测量12个样本的褶皱恢复角(wrinkle recovery angle),这种样品中有三个经向样本和三个纬向样本是在面侧弄皱,另三个经向样本和三个纬向样本是在背面弄皱的。表Ⅵ列出了反复洗涤后整理后的平均褶皱恢复角。整理剂的浓度越高,就会有更多的功能剂接合到织品上。因此,在纤维素链间形成了更多的交联,期望织品具有更好的抗褶皱性能。表Ⅵ抗-2整理后的#400纯棉织的褶皱恢复角
抗-2的浓度 | 平均褶皱恢复角(度) | ||||||
洗涤前 | 洗涤5次后 | 洗涤10次后 | 洗涤15次后 | 洗涤20次后 | 洗涤25次后 | 洗涤30次后 | |
0 | 87.0 | / | / | / | / | / | / |
2% | 88.3 | 97.2 | 100.4 | 96.0 | 97.8 | 103.0 | 99.2 |
6% | 115.4 | 111.8 | 108.4 | 111.2 | 111.0 | 111.2 | 109.8 |
10% | 120.0 | 117.8 | 114.8 | 112.1 | 114.8 | 113.8 | 112.7 |
洗涤条件与实施例Ⅲ和Ⅴ中的相同。
实施例Ⅷ
该实施例例举了pH和浸渍时间对杀生物活性的效果
基于已提出的反应机理,改性反应,即偶合反应优选酸性条件。因此在整理过程中通常优选较低的pH。反应时间也对化学改性的结果有影响。整理溶液的反应时间和PH是变化的,较低pH值的酸性条件提高了整理剂在整理后的织品上的吸液速度,发现其与期望的反应机理一致。例如,将pH从4.6降低到2.5几乎能使吸液率翻倍(表Ⅶ)。但是,延长反应时间通常对整理纤维的结果没有明显效果。表Ⅶ不同pH值和浸渍时间下处理的棉织品的杀菌性能
pH | 浸渍时间(分) | 吸液率% | 大肠杆菌的杀菌结果第一次洗涤后5或8次洗涤后 | |
2.50 | 30 | 2.83 | >5mm | 全部杀死 |
4.65 | 30 | 1.42 | >2mm | >3mm |
2.47 | 5 | 2.88 | >1mm | 全部杀死 |
4.56 | 5 | 1.64 | >2mm | >3m |
另外,还对整理后的织物进行了扩展性洗涤测试。通常,根据AATCC测试法124机洗5-8次后,再用氯漂白剂处理该织品,测定抗细菌性。样品的消毒距离仍指出该在较低pH下整理的织品具有强杀菌能力。
实施例Ⅸ
该实施例例举了抗-1处理后的整理织品的断裂强度
表Ⅷ指出了扩展的洗涤和用不同的氯浓度将杀菌性能再生后的抗-1整理织品的断裂强度保持性。织品用浓度为4%的单羟甲基-5,5-二甲基乙内酰脲的溶液整理,抗-1在织品上的吸收量是1.29%,洗涤条件与表Ⅳ中的条件相同。织品的拉伸强度用美国测试和材料学会(ASTM)的测试方法D1682进行测试。在该测试中,制备出一定量的散开的(ravelled)样本,其长度方向平行于织品的纬度,大小为25.4mm×152.4mm。以磅(1b)为单位记录织品的断裂负载。表Ⅷ某些抗-1整理的织物的断裂强度保留
Cl% | 断裂强度,1b(%存留) | |||||||
织物 | 处理前 | 处理后 | 漂白后 | 清洗5次+漂白后 | 清洗10次+漂白后 | 清洗15次+漂白后 | 清洗20次+漂白后 | |
0.01 | #400 | 31.75 | 24.30(77%) | 23.43(74%) | 23.27(73%) | 20.14(63%) | 20.34(64%) | 19.46(61%) |
#7509 | 30.71 | 32.27(100%) | 33.00(100%) | 32.41(100%) | 31.16(100%) | 31.80(100%) | 32.06(100%) | |
0.1 | #400 | 31.75 | 24.30(77%) | 22.75(74%) | 22.47(74%) | 19.63(62%) | 20.00(63%) | 19.45(61%) |
#7409 | 30.71 | 32.27(100%) | 33.27(100%) | 32.75(100%) | 31.82(100%) | 31.80(100%) | 31.86(100%) | |
0.25 | #400 | 31.75 | 24.30(77%) | 22.30(70%) | 19.32(61%) | 19.25(61%) | 20.32(64%) | 18.04(60%) |
#7409 | 30.71 | 32.27(100%) | 32.83(100%) | 33.34(100%) | 33.75(100%) | 32.38(100%) | 31.46(100%) |
应理解到上述描述只是例举性的,非限制性的。通过阅读上述说明,许多实施方案对本领域的普通技术人员而言将是很清楚。因此本发明的范围不是由上述说明确定的,而是由所附的权利要求书确定的,以及这些权利要求所赋予的等当物的全部范围。所有文章和参考文献包括专利申请和专利公开都被引入本发明作为参考文献。
Claims (32)
1.整理织品的组合物,所述组合物包括润湿剂和杂环N-卤代胺。
2.权利要求1的组合物,其中所述的杂环N-卤代胺选自:单羟甲基-5,5-二甲基乙内酰脲(MDMH),1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH);2,2,5,5-四甲基-1,3咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物;2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸,5,5-二甲基乙内酰脲2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物的单甲氧基化和双甲氧基化衍生物。
3.权利要求1的组合物,其中所述的杂环N-卤代胺是单羟甲基-5,5-二甲基乙内酰脲。
4.权利要求1的组合物,其中所述的杂环N-卤代胺是1,3-二羟甲基-5,5-二甲基乙内酰脲。
5.权利要求1的组合物,其中所述的润湿剂选自TritonX-100,SEQUAWET和AMWET。
6.权利要求1的组合物,还包括催化剂。
7.权利要求6的组合物,其中所述催化剂选自镁盐、锌盐和铵盐。
8.权利要求6的组合物,其中所述催化剂选自MgCl2、Mg(NO3)2、Zn(NO3)2和NH4NO3。
9.权利要求1的组合物,其中所述组合物pH值约为2-6。
10.制备杀微生物纤维素织物前体的方法,所述方法包括:
(a)将纤维素织物浸在包括催化剂、润湿剂和杂环N-卤代胺的水性处理溶液中;
(b)从所述纤维素织物中除去过量的处理液;
(c)干燥所述的纤维素织物;
(d)固化所述干燥后的纤维素织物;
(e)洗涤所固化后的纤维素织物以除去过量的试剂;和
(f)干燥所述的纤维素织物以除去水。
11.权利要求10的方法,其中所述纤维素织物是棉织品。
12.权利要求10的方法,其中纤维素织物是纸。
13.权利要求10的方法,其中所述杂环N-卤代胺选自:单羟甲基-5,5-二甲基乙内酰脲(MDMH),1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH);2,2,5,5-四甲基-1,3咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物;2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸,5,5-二甲基乙内酰脲2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物的单甲氧基化和双甲氧基化衍生物。
14.权利要求10的方法,其中所述杂环N-卤代胺是单羟甲基-5,5-二甲基乙内酰脲(MDMH)。
15.权利要求10的方法,其中所述杂环N-卤代胺是1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH)。
16.权利要求10的方法,其中所述润湿剂选自Triton X-100、SEQUAWET和AMWET润湿剂。
17.权利要求10的方法,其中所述催化剂选自镁盐、锌盐和铵盐。
18.权利要求10的方法,其中所述催化剂选自MgCl2、Mg(NO3)2、Zn(NO3)2和NH4NO3。
19.一种杀微生物纤维素织物前体,所述纤维素织物前体是由权利要求10的方法制备的。
20.使纤维素织物具有杀微生物性的方法,所述方法包括:
(a)用卤化溶液洗涤杀微生物纤维织物前体,所述杀微生物纤维织物前体是根据权利要求10制备的;和
(b)干燥所述处理后的杀微生物纤维素织物以除去水。
21.用权利要求20的方法处理后的杀微生物纤维织物用作织物材料。
22.用权利要求20的方法处理后的棉织品用作织物材料。
23.制备杀微生物纤维素/聚酯织物前体的方法,所述方法包括:
(a)将纤维素/聚酯织物浸在包括催化剂、润湿剂和杂环N-卤代胺的水性处理溶液中;
(b)从所述纤维素/聚酯织物中除去过量的处理液;
(c)干燥所述的纤维素/聚酯织物;
(d)固化所述干燥后的纤维素/聚酯织物;
(e)洗涤所固化后的纤维素/聚酯织物以除去过量的试剂;和
(f)干燥所述的纤维素/聚酯织物以除去水。
24.权利要求23的方法,其中所述纤维素/聚酯织物是棉/聚酯织品。
25.权利要求23的方法,其中所述杂环N-卤代胺选自:单羟甲基-5,5-二甲基乙内酰脲(MDMH),1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH);2,2,5,5-四甲基-1,3咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物;2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸,5,5-二甲基乙内酰脲2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物的单甲氧基化和双甲氧基化衍生物。
26.权利要求23的方法,其中所述杂环N-卤代胺是单羟甲基-5,5-二甲基乙内酰脲(MDMH)。
27.权利要求23的方法,其中所述杂环N-卤代胺是1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH)。
28.一种杀微生物纤维素/聚酯织物前体,所述纤维素/聚酯织物前体是由权利要求23的方法制备的。
29.一种使纤维素/聚酯织物具有杀微生物性的方法,所述方法包括:
(a)用卤化溶液洗涤杀微生物纤维素/聚酯织物前体,所述杀微生物纤维素/聚酯织物前体是根据权利要求23方法制备的;和
(b)干燥所述处理后的杀微生物纤维素/聚酯织物以除去水。
30.用权利要求29方法处理的杀微生物纤维素/聚酯织物用作织物材料。
31.用权利要求29方法处理后的棉/聚酯织品用作织物材料。
32.织物材料,其具有其上共价结合杂环N-卤代胺的纤维素表面。
33.权利要求32的织物材料,其中所述杂环N-卤代胺选自:单羟甲基-5,5-二甲基乙内酰脲(MDMH),1,3-二羟甲基-5,5-二甲基乙内酰脲(DMDMH);2,2,5,5-四甲基-1,3咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物;2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸,5,5-二甲基乙内酰脲2,2,5,5-四甲基-1,3-咪唑啉-4-酮,6,6-二甲基-1,3,5-三嗪-2,4-二酮,4,4,5,5-四甲基-1,3-咪唑啉-2-酮,氰尿酸和5,5-二甲基乙内酰脲的单羟甲基化和双羟甲基化衍生物的单甲氧基化和双甲氧基化衍生物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/713,406 US5882357A (en) | 1996-09-13 | 1996-09-13 | Durable and regenerable microbiocidal textiles |
US08/713,406 | 1996-09-13 |
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CNB2004100050346A Division CN1291101C (zh) | 1996-09-13 | 1997-09-12 | 耐久的、可再生的杀微生物织物 |
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CNB2004100050346A Expired - Fee Related CN1291101C (zh) | 1996-09-13 | 1997-09-12 | 耐久的、可再生的杀微生物织物 |
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CNB2004100050346A Expired - Fee Related CN1291101C (zh) | 1996-09-13 | 1997-09-12 | 耐久的、可再生的杀微生物织物 |
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US (2) | US5882357A (zh) |
EP (1) | EP0942649B1 (zh) |
JP (1) | JP2001500513A (zh) |
KR (1) | KR100519551B1 (zh) |
CN (2) | CN1145415C (zh) |
AT (1) | ATE448685T1 (zh) |
AU (1) | AU734955B2 (zh) |
BR (1) | BR9711787A (zh) |
CA (1) | CA2265851C (zh) |
DE (1) | DE69739661D1 (zh) |
ES (1) | ES2334954T3 (zh) |
HK (1) | HK1068658A1 (zh) |
ID (1) | ID24357A (zh) |
NO (1) | NO318855B1 (zh) |
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CN100451125C (zh) * | 2000-02-17 | 2009-01-14 | 苏拉化学有限公司 | 制备用作生物材料、特别是用在显微成形外科中的成形微生物纤维素的方法和装置 |
US10542756B2 (en) | 2013-08-29 | 2020-01-28 | Green Impact Holding Ag | Disinfectant composition for textile and related substrates, and method of treating a substrate to provide disinfecting antibacterial, antiviral and antifungal, wash durable, optionally enhanced with multifunctional properties |
CN105658245A (zh) * | 2013-08-29 | 2016-06-08 | 绿色影响控股公司 | 用于布料及相关基材的消毒剂组合物与处理基材,以提供消毒抗菌,抗病毒、抗真菌、耐洗,及任选的增强的多功能特性的方法。 |
US11134686B2 (en) | 2013-08-29 | 2021-10-05 | Green Impact Holding Ag | Disinfectant composition for textile and related substrates, and method of treating a substrate to provide disinfecting antibacterial, antiviral and antifungal, wash durable, optionally enhanced with multifunctional properties |
CN105658245B (zh) * | 2013-08-29 | 2019-05-07 | 绿色影响控股公司 | 处理布料基材的方法、经处理的布料基材及其用途 |
CN110106697A (zh) * | 2013-08-29 | 2019-08-09 | 绿色影响控股公司 | 处理布料基材的方法 |
TWI705172B (zh) * | 2015-02-27 | 2020-09-21 | 瑞士商衛生有限公司 | 具有抗微生物性能之布料 |
CN107567513B (zh) * | 2015-02-27 | 2020-07-14 | 生活保卫股份公司 | 具有抗微生物性能之布料 |
CN111621981A (zh) * | 2015-02-27 | 2020-09-04 | 生活保卫股份公司 | 具有抗微生物性能之布料 |
CN111691181A (zh) * | 2015-02-27 | 2020-09-22 | 生活保卫股份公司 | 具有抗微生物性能之布料 |
CN111705503A (zh) * | 2015-02-27 | 2020-09-25 | 生活保卫股份公司 | 具有抗微生物性能之布料 |
CN112030552A (zh) * | 2015-02-27 | 2020-12-04 | 生活保卫股份公司 | 具有抗微生物性能之布料 |
CN107567513A (zh) * | 2015-02-27 | 2018-01-09 | 绿色影响控股公司 | 具有抗微生物性能之布料 |
CN108884626A (zh) * | 2015-12-30 | 2018-11-23 | 绿色影响控股公司 | 具有抗微生物性能的布料 |
CN108884626B (zh) * | 2015-12-30 | 2021-06-08 | 生活保卫股份公司 | 具有抗微生物性能的布料 |
Also Published As
Publication number | Publication date |
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ES2334954T3 (es) | 2010-03-17 |
DE69739661D1 (de) | 2009-12-31 |
BR9711787A (pt) | 1999-08-24 |
WO1998010648A1 (en) | 1998-03-19 |
EP0942649A1 (en) | 1999-09-22 |
KR20000036070A (ko) | 2000-06-26 |
HK1068658A1 (en) | 2005-04-29 |
AU4428697A (en) | 1998-04-02 |
NO991173D0 (no) | 1999-03-10 |
CA2265851A1 (en) | 1998-03-19 |
ID24357A (id) | 2000-07-13 |
NO991173L (no) | 1999-05-11 |
US6077319A (en) | 2000-06-20 |
CN1519419A (zh) | 2004-08-11 |
NO318855B1 (no) | 2005-05-18 |
CN1145415C (zh) | 2004-04-14 |
JP2001500513A (ja) | 2001-01-16 |
CN1291101C (zh) | 2006-12-20 |
ATE448685T1 (de) | 2009-12-15 |
KR100519551B1 (ko) | 2005-10-13 |
CA2265851C (en) | 2011-01-04 |
EP0942649B1 (en) | 2009-11-18 |
US5882357A (en) | 1999-03-16 |
AU734955B2 (en) | 2001-06-28 |
EP0942649A4 (en) | 2000-10-11 |
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