CN103704264B - 一种消毒清洁剂 - Google Patents
一种消毒清洁剂 Download PDFInfo
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Abstract
本发明公开了一种消毒清洁剂,包括如下成分:过氧化氢:0.1-6%(w/w%)、过氧乙酸:0.01-0.6%(w/w%)、季胺盐类:0.01-2%(w/w%)、表面活性剂:0.01-1%(w/w%)、碱:1-3%(w/w%)、焦磷酸钠:0-1%(w/w%)、水:90-96%(w/w%);消毒清洁剂的PH值为7.0-9.9。本发明具有低毒、低腐蚀性、无刺激性气味和快速、广谱、高效杀菌,杀病毒和孢子的优点。
Description
技术领域
本发明涉及一种消毒清洁剂,适用于各种公共场所、家庭使用。
背景技术
目前,公共用的消毒清洁剂,除了某些加入漂白粉型的消毒清洁剂,具有广谱杀菌、杀病毒外,其它类型的消毒清洁剂都不具备这种广谱消毒作用。而漂白粉型消毒清洁剂,具有比较强的腐蚀性,它们对家用电器和公共场所的仪器设备都有不同程度的危害,会加速它们的锈蚀。除了具有强烈的腐蚀性外,漂白粉型消毒清洁剂还有两个重要的缺点:1.它和环境中的有机化合物反应会产生有机氯化合物,据有关研究表明,其中一些有机氯化合物有较强的致癌作用;2.产生对人身体健康不利、具有较强刺激性的气味,尤其是在大面积使用时,这气味已远超出人们所能忍受的范围。过氧化氢由于其在低浓度时表现出低的反应活性,不能快速杀死细菌,见表一。
表一:过氧化氢的消毒测试结果。结果表明,2%的过氧化氢不能用于快速消毒。
而高浓度的过氧化氢不但有强烈的腐蚀性,对皮肤也有强烈的烧灼作用。所以,过氧化氢不能单独作为家庭和公共场所的常用和大面积使用的消毒剂。常态过氧乙酸由于其强烈的刺激性气味,也不适合在家庭和公共场所广泛使用。为此,发展一种既能快速杀死细菌,病毒和孢子,又无毒,低腐蚀性和无刺激性气味的广谱消毒清洁剂,是改善家庭和公共卫生的当务之急。尤其在瘟疫、流感可能爆发地和重灾区,大面积使用无毒,低腐蚀性,无刺激性气味的广谱消毒清洁剂,既不影响救灾人员和被救人员的健康,又能迅速阻止瘟疫、流感的暴发和传播。
发明内容
本发明的目的在于提供一种低毒、低腐蚀性、无刺激性气味的消毒清洁剂。
本发明的技术解决方案是:
消毒活性物是由过氧化氢和过氧乙酸的共轭碱,即相应的负离子组成。在碱性条件下(pH7.1-9.9,最佳使用pH在9.0-9.5之间),过氧乙酸将转变为具有更高氧化性的亚稳态负离子(表二),从而具备快速消毒作用。由于过氧乙酸负离子是非挥发性的,从而消除了过氧乙酸那令人难以接受,并使人头晕的强烈刺激性气味。
过氧乙酸是一弱有机酸,它在水溶液里存在着反应式(1)所示的离解平衡。
随着溶液pH的增加,过氧乙酸浓度将会降低,而其共轭碱,过氧乙酸负离子浓度将增加,如图1所示。在pH达到8.2时,过氧乙酸和其共轭碱的浓度达到相等。当pH达到9.5时,过氧乙酸浓度只有原酸态时浓度的5%。大于95%的过氧乙酸将以其非挥发性的共轭碱形态存在于水溶液中。在总过氧乙酸(包括其共轭碱态)浓度不变的情况下,挥发性的过氧乙酸浓度已经显著降低,从而消除了由过氧乙酸所组成的消毒清洁剂,由于过氧乙酸的挥发而产生的强刺激性气味。
氧化消毒能力试验:当过氧乙酸变成其共轭碱,即过氧乙酸负离子,其氧化性能力和消毒能力是否降低,这是我们发明的关键所在。
氧化能力测试:我们的研究结果表面,当过氧乙酸在碱性溶液中,其对硫代硫酸钠的氧化性将大于其在酸性中的氧化性,如图2所示。
图中结果表明,硫代硫酸钠在碱性溶液中,30秒钟内将被完全氧化掉。在这30秒内,大于75%的过氧乙酸被消耗掉。据检测数据依照计量化学推算,硫代硫酸钠被彻底氧化掉主要是由于和过氧乙酸负离子的反应。此时,过氧化氢所作的贡献,要小于10%。而在酸性条件下,硫代硫酸钠首先被不完全氧化而转化成其它具有还原特性的化合物(图中保留时间在1.6分钟左右),这些化合物将继续被过氧乙酸和过氧化氢氧化掉。当反应持续到大于5分钟后,这些化合物才能被完全氧化掉。而在这5分钟时,仅有小于50%的过氧乙酸被消耗掉。其余用于氧化氧化硫代硫酸钠和其中间反应产物的氧化剂,是过氧化氢。在整个氧化反应中,过氧化氢所作的贡献要大于30%。这些对比结果表明,在碱性溶液中,过氧乙酸的氧化性要大于在酸性溶液中。在氧化亚硫酸钠的反应中,如溶液是碱性,亚硫酸钠在30秒内就被氧化完,其主要贡献来源于过氧乙酸负离子(约90%),过氧化氢的贡献在10%左右。但在酸性溶液中,亚硫酸钠被完全氧化需要略大于30秒,其主要贡献是来源于过氧化氢(约70%),而过氧乙酸的贡献仅占约30%。
氧化抗坏血酸,L-asorbicacid(LSA)的实验,也证实了过氧乙酸在碱性溶液表现出更强的氧化性,如图3所示。在碱性溶液中,LSA在5分钟内被完全氧化掉,而在酸性溶液中,5分钟内仅有约50%的LSA被氧化掉。在这个反应中,无论是在酸性和碱性状态,溶液中的过氧化氢浓度几乎保持恒定。这表明,氧化LSA的主要贡献是过氧乙酸或过氧乙酸负离子。
消毒测试:实验结果表明,我们发明的消毒剂,可迅速杀死细菌,病毒和孢子,见下表。
表:消毒试验结果,接触时间1-3分钟。
使过氧乙酸在碱性溶液中保持稳定:
过氧乙酸在水溶液中不稳定,容易分解成醋酸和氧气(反应式2和3)。
在水溶液中,过氧乙酸的分解模式主要有两种,一是金属离子催化分解,二是水解分解。随着溶液pH的增加,过氧乙酸的水解分解速度会显著增加。如用氢氧化钠调整其pH至9.3左右,一分钟内,约有80%的过氧乙酸被分解掉,5分钟时,大于90%的过氧乙酸被分解掉。图四列出过氧乙酸在pH=9.3的水溶液中的分解状况。
过氧乙酸的快速分解,会使消毒剂丧失消毒能力。因此,保持过氧乙酸在碱性溶液中的相对稳定,至关重要。当用碳酸钠调整溶液的pH,过氧乙酸可保持相对稳定,10分钟内可保持大于90%过氧乙酸不被分解(图四)。加焦磷酸钠等金属离子络合剂,也可保持过氧乙酸相对稳定。由于我们的发明采用即时二合一应用技术,只要能保持过氧乙酸相对稳定,就能保证在杀死毒物前,保留足够浓度的过氧乙酸/过氧乙酸负离子。这一点非常重要,因为杀死某些毒物,如孢子类细菌,需要一定的接触时间,通常需要3-5分钟。而我们的发明,可以保证在10分钟内,使总过氧乙酸(包括它的转化成的氧乙酸负离子)的损失小于10%。
离子对试剂和相转移催化剂:
离子对试剂和相转移催化剂是氢氧化四丁铵或类似的季铵盐类化合物。在环境中,或在实际应用时,毒物总是可能被污染物包围着,有些污染物还是非水溶性的。这意味着消毒剂很难迅速穿透非水溶性污染物而到达毒物表面。如使用离子对试剂和过氧乙酸负离子形成离子对(反应式4),并在相转移催化剂的帮助下,使过氧乙酸负离子能迅速到达毒物表面,并协助过氧乙酸负离子穿透某些毒物外表保护层,从而杀死毒物。
消毒清洁剂组成:
包括如下成分:
消毒活性物:过氧化氢:0.1-6%(w/w%),过氧乙酸:0.01-0.6%(w/w%)。
离子对试剂和相转移催化剂:0.01-2%(w/w%)。
表面活性剂:0.01-1%(w/w%)。
碱:0.1-3%(w/w%)。
稳定剂:0-1%(w/w%)。
水:90-96%(w/w%)。
消毒清洁剂的PH值为7.1-9.9,正常使用pH值在9-9.5之间。
本发明的进一步改进在于:使消毒活性物过氧化氢和过氧乙酸在碱性条件下(pH值为7.1-9.9,最佳使用pH值在9-9.5之间),变为高氧化性亚稳态负离子而具备快速消毒作用和使过氧乙酸变成无挥发性状态,从而消除过氧乙酸的强烈刺激性气味。
本发明的进一步改进在于:离子对试剂和相转移催化剂为氢氧化四丁铵或十六烷基三甲基溴化铵或氢氧化四丁铵与十六烷基三甲基溴化铵的混合物,它们将帮助消毒活性物在复杂环境中迅速和毒物接触从而达到快速消毒之目的。
本发明的进一步改进在于:表面活性剂为磷酸类表面活性剂和磺酸类表面活性剂的混合物,磷酸类表面活性剂为1-Hydroxyethylidene-1,1,-diphosphonicacid和Dextrol?OC-40PhosphateEster,磺酸类表面活性剂为十二烷基磺酸钠和十二烷基磺酸氨。
本发明的进一步改进在于:碱为氢氧化钠、碳酸钠、磷酸钠以及有机碱,有机碱为氢氧化四丁铵,苯乙胺或氢氧化胺,这些化合物将使过氧化氢和过氧乙酸变为其相应的负离子。
本发明的进一步改进在于:稳定剂是金属离子络合剂,如8-羟基喹啉、焦磷酸钠、1-Hydroxyethylidene-1,1,-diphosphonicacid和EDTA,碳酸钠也能起到稳定过氧乙酸负离子的作用。
由于本发明具有低毒,低腐蚀性,和无刺激性气味等优良特性,使其可以在公共场所和家庭大量,大面积使用,如各类车站,机场候机厅,医院,饮食业和家庭的卫生。尤其在流感,瘟疫发生区域大量使用,可以快速杀死病毒,细菌和孢子,从而显著降低流感和瘟疫的爆发和传播。
附图说明:
图1为过氧乙酸在水溶液中的离解率随pH改变而变化,PAA指过氧乙酸,PAA-指过氧乙酸负离子;
图2为当17.4毫摩尔过氧乙酸,64.8毫摩尔的过氧化氢和5.0毫摩尔的硫代硫酸钠(STS)反应,硫代硫酸钠及其降解产物的消失与时间的关系,酸性pH小于2,碱性pH等于9.3;
图3为6毫摩尔抗坏血酸(LSA)和64.8毫摩尔过氧化氢,17.8毫摩尔过氧乙酸在水溶液中的反应.酸性溶液pH=2.3.碱性溶液pH=9.4;
图4为在溶液pH=9.3左右,过氧乙酸保留率和时间的关系,原始浓度,过氧乙酸是0.2%,过氧化氢是4%,溶液pH调整用氢氧化钠或磷酸钠溶液,稳定PAA可用碳酸钠或加稳定剂,如焦磷酸钠,PAA定量分析用离子色谱。
具体实施方式:
为了加深对本发明的理解,下面将结合实施例对本发明作进一步详述,该实施例仅用于解释本发明,并不构成对本发明保护范围的限定。
一种消毒清洁剂,包括如下成分:
消毒活性物:过氧化氢:0.1-6%(w/w%),过氧乙酸:0.01-0.6%(w/w%)。
离子对试剂和相转移催化剂:0.01-2%(w/w%)。
表面活性剂:0.01-1%(w/w%)。
碱:0.1-3%(w/w%)。
稳定剂:0-1%(w/w%)。
水:90-96%(w/w%)。
消毒清洁剂的PH值为7.1-9.9,正常使用pH值在9-9.5之间。使消毒活性物过氧化氢和过氧乙酸在碱性条件下(pH值为7.1-9.9,最佳使用pH值在9-9.5之间),变为高氧化性亚稳态负离子而具备快速消毒作用和使过氧乙酸变成无挥发性状态,从而消除过氧乙酸的强烈刺激性气味。离子对试剂和相转移催化剂为氢氧化四丁铵或十六烷基三甲基溴化铵或氢氧化四丁铵与十六烷基三甲基溴化铵的混合物,它们将帮助消毒活性物在复杂环境中迅速和毒物接触从而达到快速消毒之目的。表面活性剂为磷酸类表面活性剂和磺酸类表面活性剂的混合物,磷酸类表面活性剂为1-Hydroxyethylidene-1,1,-diphosphonicacid和Dextrol?OC-40PhosphateEster,磺酸类表面活性剂为十二烷基磺酸钠和十二烷基磺酸氨。碱为氢氧化钠、碳酸钠、磷酸钠以及有机碱,有机碱为氢氧化四丁铵,苯乙胺或氢氧化胺,这些化合物将使过氧化氢和过氧乙酸变为其相应的负离子。稳定剂是金属离子络合剂,如8-羟基喹啉、焦磷酸钠、1-Hydroxyethylidene-1,1,-diphosphonicacid和EDTA,碳酸钠也能起到稳定过氧乙酸负离子的作用。
一种消毒清洁剂,包括如下A和B两组份:
组份A包括:消毒活性物:如过氧化氢:0.1-10%(w/w%),过氧乙酸:0.01-0.8%(w/w%),金属离子络合物:如HEDPA、焦磷酸:0.01-1%(w/w%),和水:90-94%(w/w%)。
组份B包括:离子对试剂和相转移催化剂:0.01-2%(w/w%)、表面活性剂:0.01-1%(w/w%)、碱:0.1-3%(w/w%)和水:90-96%(w/w%)。
消毒清洁剂的PH值为7.0-9.9,最佳使用pH在9-9.5之间。
其中,消毒活性物为过氧化氢和过氧乙酸;离子对试剂和相转移催化剂为氢氧化四丁铵(TBAH)或十六烷基三甲基溴化铵;表面活性剂为十二烷基磺酸钠(SDS)或1-Hydroxyethylidene-1,1,-diphosphonicacid(HEDPA);碱为无机碱,如氢氧化钠,氢氧化胺,碳酸钠,磷酸钠和有机碱,如氢氧化四丁铵,苯乙胺。稳定剂为:焦磷酸,1-Hydroxyethylidene-1,1,-diphosphonicacid(HEDPA)。
制备:根据表中所给浓度配成组成A和组成B。
本发明采用过氧化氢,过氧乙酸,离子对试剂/表面活性剂/相转移催化剂(季胺盐),水等,通过科学配比,使其具有快速杀死细菌,病毒和孢子的功能。由于配方科学化,本广谱消毒清洁剂具有低腐蚀性,低毒性,无刺激性气味和低残留等环保特征。使其能在各种公共场所,家庭使用。由于本发明具有低毒,低腐蚀性,和无刺激性气味等优良特性,使其可以在公共场所和家庭大量,大面积使用,如各类车站,机场候机厅,医院,饮食业和家庭的卫生。尤其在流感,瘟疫发生区域大量使用,可以快速杀死病毒,细菌和孢子,从而显著降低流感和瘟疫的爆发和传播。
Claims (4)
1.一种消毒清洁剂,其特征是:包括如下成分:
消毒活性物:过氧化氢:0.1-6%(w/w%),过氧乙酸:0.01-0.6%(w/w%);
离子对试剂和相转移催化剂:0.01-2%(w/w%);
表面活性剂:0.01-1%(w/w%);
碱:0.1-3%(w/w%);
稳定剂:0-1%(w/w%);
水:90-96%(w/w%);
消毒清洁剂的pH值为7.1-9.9;
所述离子对试剂和相转移催化剂为氢氧化四丁铵或十六烷基三甲基溴化铵或氢氧化四丁铵与十六烷基三甲基溴化铵的混合物;所述稳定剂是金属离子络合剂,所述金属离子络合剂为8-羟基喹啉、焦磷酸钠、1-羟基亚乙基-1,1,二膦酸和乙二胺四乙酸。
2.根据权利要求1所述的一种消毒清洁剂,其特征是:使消毒活性物过氧化氢和过氧乙酸在碱性条件下变为高氧化性亚稳态负离子而具备快速消毒作用和使过氧乙酸变成无挥发性状态,从而消除过氧乙酸的强烈刺激性气味,碱性条件为pH值为7.1-9.9。
3.根据权利要求1所述的一种消毒清洁剂,其特征是:所述表面活性剂为磷酸类表面活性剂和磺酸类表面活性剂的混合物,所述磷酸类表面活性剂为1-羟基亚乙基-1,1,二膦酸和DextrolOC-40膦酸脂类表面活性剂,所述磺酸类表面活性剂为十二烷基磺酸钠和十二烷基磺酸胺。
4.根据权利要求1所述的一种消毒清洁剂,其特征是:所述碱为氢氧化钠、碳酸钠、磷酸钠以及有机碱,所述有机碱为氢氧化四丁铵、苯乙胺或氢氧化胺。
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