CN102308810B - 杀微生物剂组合物 - Google Patents

杀微生物剂组合物 Download PDF

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CN102308810B
CN102308810B CN201110230484.5A CN201110230484A CN102308810B CN 102308810 B CN102308810 B CN 102308810B CN 201110230484 A CN201110230484 A CN 201110230484A CN 102308810 B CN102308810 B CN 102308810B
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benzisothiazole
microbicide
methyl isophthalic
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J·W·阿什莫尔
B·J·埃尔阿马
B·希尔
R·莱维
K·帕里克
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Abstract

本发明涉及一种杀微生物剂组合物，其包含以下组分：(a)N-甲基-1，2-苯并异噻唑啉-3-酮；(b)碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵。

Description

杀微生物剂组合物
本申请是申请人于2008年7月16日提交的申请号为200810131638.3、发明名称为“杀微生物剂组合物”的发明专利申请的分案申请。
技术领域
本发明涉及选择的杀微生物剂的协同组合，所述组合的活性要大于在单独的杀微生物剂上观察到的活性。
背景技术
在一些情况下，由于市售的杀微生物剂对某些种类的微生物(例如对一些杀微生物剂具有抗性的微生物)的活性很差，或者由于剧烈的环境条件，即使采用高施用浓度，所述市售的杀微生物剂也无法提供有效的微生物控制。有时人们使用不同杀微生物剂的组合对特别的最终应用环境提供微生物的总体控制。例如，美国专利申请公开第2007/0078118号揭示了N-甲基-1，2-苯并异噻唑啉-3-酮(MBIT)与其它的生物杀伤剂的协同组合。但是，人们需要对各种微生物菌株具有提高的活性的另外的杀微生物剂的组合，以提供对微生物有效的控制。另外，出于环境和经济效益的考虑，人们需要包含较低含量单独的杀微生物剂的组合。本发明所解决的问题是提供这种杀微生物剂的另外的组合。
发明内容
本发明涉及包含以下组分的杀微生物剂组合物：(a)N-甲基-1，2-苯并异噻唑啉-3-酮；(b)选自以下的至少一种杀微生物剂：月桂酰精氨酸乙酯盐酸盐(ethyl lauroyl arginate hydrochloride)、氯化(柯卡酰氨丙基-N-2-羟基乙基氨基甲酰基甲基二甲基铵)(cocamidopropyl-N-2-hydroxyethylcarbamoylmethyl dimethyl ammonium chloride)、2-氨基乙醇铜(II)和氯化二癸基二甲基铵、碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵、2-氨基乙醇铜(II)、单月桂酸甘油酯、单月桂酸丙二醇酯、以及辛酸丙二醇酯。
具体实施方式
在本文中，除非上下文有另外的说明，以下术语具有所指的含意。“MBIT”是N-甲基-1，2-苯并异噻唑啉-3-酮。术语“杀微生物剂”表示能够在某一区域杀死微生物、抑制微生物生长或控制微生物生长的化合物；杀微生物剂包括杀菌剂，杀真菌剂和杀藻剂。术语“微生物”包括例如真菌(例如酵母菌和霉菌)，细菌和藻类。术语“区域”表示易受微生物污染的工业装置或产品。在本说明书中使用以下缩写：ppm＝百万分之一重量份(重量/重量)，mL＝毫升，ATCC＝美国典型培养物保藏所(American Type CultureCollection)，MIC＝最低抑制浓度。除非另外说明，温度的单位是摄氏度(℃)，百分数以重量计。有机杀微生物剂的含量以活性组分为基准计，单位为ppm(w/w)。
出乎意料地发现，本发明的组合物能够以低于单独的杀微生物剂的组合活性组分含量提供提高的杀微生物效率。在所述组合物中可以包含超出权利要求中所列范围的其它的杀微生物剂。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮和月桂酰精氨酸乙酯盐酸盐。较佳的是，月桂酰精氨酸乙酯盐酸盐与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶94至1∶0.0137。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮和氯化(柯卡酰氨丙基-N-2-羟基乙基氨基甲酰基甲基二甲基铵)。较佳的是，氯化(柯卡酰氨丙基-N-2-羟基乙基氨基甲酰基甲基二甲基铵)与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶188至1∶0.0022。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮以及2-氨基乙醇铜(II)和氯化二癸基二甲基铵。较佳的是，2-氨基乙醇铜(II)和氯化二癸基二甲基铵与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶176至1∶0.08。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮以及碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵。较佳的是，碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶227至1∶0.179。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮和2-氨基乙醇铜(II)。较佳的是，2-氨基乙醇铜(II)与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶375至1∶0.004。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮和单月桂酸甘油酯。较佳的是，单月桂酸甘油酯与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶0.143至1∶0.0004。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮和单月桂酸丙二醇酯。较佳的是，单月桂酸丙二醇酯与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶0.286至1∶0.0286。
在本发明的一个实施方式中，所述抗微生物组合物包含N-甲基-1，2-苯并异噻唑啉-3-酮和辛酸丙二醇酯。较佳的是，辛酸丙二醇酯与N-甲基-1，2-苯并异噻唑啉-3-酮的重量比为1∶0.442至1∶0.0018。
本发明组合物中的杀微生物剂可直接使用，或者可首先使用溶剂或固体载体进行配制。合适的溶剂包括例如水；二元醇，例如乙二醇、丙二醇、二甘醇、二丙甘醇、聚乙二醇和聚丙二醇；乙二醇醚；醇，例如甲醇、乙醇、丙醇、苯乙醇和苯氧基丙醇；酮，例如丙酮和甲基乙基酮；酯，例如乙酸乙酯、乙酸丁酯、三乙酰基柠檬酸酯、以及三乙酸甘油酯；碳酸酯，例如碳酸异丙烯酯和碳酸二甲酯；以及它们的混合物。优选的溶剂选自水、二元醇、二醇醚、酯及其混合物。合适的固体载体包括例如环糊精、二氧化硅、硅藻土、蜡、纤维素材料、碱金属和碱土(例如钠、镁、钾)金属盐(例如氯化物、硝酸盐、溴化物、硫酸盐)和炭。
当杀微生物剂用溶剂配制时，该制剂可任选包含表面活性剂。当这种制剂包含表面活性剂时，它们通常为乳液浓缩物、乳液、微乳液浓缩物或微乳液的形式。乳液浓缩物在加入足量的水的时候形成乳液。微乳液浓缩物在加入足量的水的时候形成微乳液。这些乳液和微乳液浓缩物是本领域众所周知的；优选这些制剂不含表面活性剂。关于制备各种微乳液和微乳液浓缩物的更广泛和具体的细节可参见美国专利第5444078号。
还可以分散体的形式配制杀微生物剂组分。分散体的溶剂组分可以是有机溶剂或水，优选的是水。这些分散体可包含辅助剂，例如助溶剂、增稠剂、防冻剂、分散剂、填料、颜料、表面活性剂、生物分散剂、磺基丁二酸盐、萜烯、呋喃酮、聚阳离子、稳定剂、污垢抑制剂和抗腐蚀添加剂。
当两种杀微生物剂都各自先用溶剂配制时，用于第一杀微生物剂的溶剂可与用来配制另一种市售杀微生物剂的溶剂相同或不同，但是优选水用于大多数工业生物杀伤剂应用。较佳的是，这两种溶剂可混溶。
本领域技术人员将会意识到，可以将本发明的杀微生物剂依次或同时施加到某一区域，或者在施加到该区域之前混合。较佳的是，将第一杀微生物剂和第二杀微生物剂同时或依次施加到某一区域。当所述杀微生物剂同时或依次施加到某区域时，每种单独的组分可包含辅助剂，例如溶剂、增稠剂、防冻剂、着色剂、螯合剂(例如乙二胺四乙酸、乙二胺二琥珀酸、亚氨基二琥珀酸及其盐)、分散剂、表面活性剂、生物分散剂、磺基丁二酸酯、萜烯、呋喃酮、聚阳离子、稳定剂、污垢抑制剂和抗腐蚀添加剂。
可通过在易受微生物侵袭的区域上或之内引入抗菌有效量的本发明杀微生物组合物来抑制微生物或者更高级的水生生物(例如原生动物，无脊椎动物，苔藓动物，腰鞭毛类，甲壳类动物，软体动物等)的生长。合适的区域包括例如：工业工艺水；电涂覆沉积系统；冷却塔；空气洗涤器；气体洗涤器；矿物浆液；废水处理系统；装饰用喷泉；反渗透过滤器；超滤装置；压舱水；蒸发冷凝器；热交换器；纸浆和纸加工液以及添加剂；淀粉；塑料；乳液；分散体；油漆；胶乳；涂料，例如清漆；建筑产品，例如胶泥、填漏材料和密封剂；建筑粘合剂，例如陶瓷粘合剂、地毯背衬粘合剂和层叠粘合剂；工业用或消费用粘合剂；摄影用化学品；印刷液；家用产品，例如卫生间和厨房清洁剂以及清洁擦拭用品；化妆品；化妆用品；洗发露；肥皂；洗涤剂；工业清洁剂；地板蜡；洗衣房漂洗水；金属加工液；输送带润滑剂；液压机液体；皮革和皮革制品；织物；织物产品；木材和木材产品，例如胶合板、硬纸板、刨花板、叠层梁、取向的绞合板、硬纸板和碎料板；石油加工液；燃料；油田液，例如注入水、断裂液和钻探泥浆；农业辅助剂保存；表面活性剂保存；医疗器件；诊断试剂保存；食物保存，例如塑料或纸质食物包装；食物、饮料、以及工业处理巴氏灭菌器；抽水马桶；娱乐用水；池塘；和温泉。
优选用本发明的杀微生物剂组合物在选自以下的一个或多个区域抑制微生物的生长：矿物浆液；纸浆和纸加工液以及添加剂；淀粉；乳液；分散体；油漆；胶乳；涂料；建筑粘合剂，例如陶瓷粘合剂、地毯背衬粘合剂；摄影用化学品；印刷液；家用产品，例如卫生间和厨房清洁剂以及清洁擦拭用品；化妆品；化妆用品；洗发露；肥皂；洗涤剂；工业清洁剂；地板蜡；洗衣房漂洗水；金属加工液；织物产品；木材和木材产品；农业辅助剂保存；表面活性剂保存；诊断试剂保存；食物保存；食物、饮料、以及工业程序的巴氏灭菌器。
用来抑制或控制某一区域微生物生长所需的本发明组合物的具体用量取决于需要保护的特定区域。通常来说，如果在某区域中提供的本发明组合物的异噻唑啉酮组分含量为0.1-1000ppm，则该组合物的量足以控制微生物生长。较佳的是在该区域中组合物的异噻唑啉酮组分含量至少为0.5ppm，更优选至少为4ppm，最优选至少为10ppm。较佳的是存在于该区域中的组合物的异噻唑啉酮组分的含量不超过1000ppm，更优选不超过500ppm，最优选不超过200ppm。
实施例
材料和方法
通过对宽范围的化合物浓度和比例进行测试，说明了本发明的组合的协同作用。
一种协同作用的测定是Kull，F.C.；Eisman，P.C.；Sylwestrowicz，H.D.和Mayer，R.L.在应用微生物学(Applied Microbiology)9：538-541(1961)中提出的工业可接受的方法，该方法使用由下式算得的比例：
Qa/QA+Qb/QB＝协同指数(“SI”)
式中：
QA＝单用时能够产生终点的化合物A(第一组分)的浓度(化合物A的MIC)，其单位为ppm。
Qa＝以混合物形式时能够产生终点的化合物A的浓度，其单位为ppm。
QB＝单用时能够产生终点的化合物B(第二组分)的浓度(化合物B的MIC)，其单位为ppm。
Qb＝以混合物形式时能够产生终点的化合物B的浓度，其单位为ppm。
当Qa/QA和Qb/QB之和大于1时，说明具有拮抗作用。当它们之和等于1时，说明具有叠加作用，当小于1时，说明具有协同作用。SI越小，特定混合物所显示的协同作用越大。抗菌化合物的最小抑制浓度(MIC)是在一组特定条件下测得的能够阻止所加入的微生物生长的最低浓度。
使用标准微量滴定板，用设计能使试验微生物最优生长的培养基进行协同试验。细菌试验采用添加了0.2％葡萄糖和0.1％的酵母提取物的矿物盐培养基(M9GY培养基)；酵母菌和霉菌试验使用马铃薯葡萄糖肉汤(PotatoDextrose Broth)(PDB培养基)。在此方法中，在包含各种浓度的MBIT的情况下进行高分辨MIC试验检测了许多种杀微生物剂的组合。高分辨MIC通过以下步骤进行：在一排微量滴定板中加入各种量的杀微生物剂，用自动液体操作系统进行10倍连续稀释，获得从2ppm至10000ppm活性组分的一系列活性组分的终点。
测定了本发明的组合下表所述的一些微生物的协同作用。所用细菌的浓度约为5×106细菌/毫升，酵母菌和霉菌的浓度为5×105真菌/毫升。这些微生物代表了许多消费品和工业应用中的天然污染。在25℃(酵母菌和霉菌)或30℃(细菌)培养不同时间后目视观察微量滴定板上微生物生长情况确定MIC。
显示本发明MBIT组合的协同作用的试验结果列于以下表1-8中。在各测试中，第二组分(B)是MBIT，第一组分(A)是其它的市售杀微生物剂。各表显示了MBIT和其它组分的具体组合；在培育时间测得的对抗微生物的结果；通过MIC测定单用MBIT(QB)，单用其它组分(QA)，在混合物中的MBIT(Qb)以及在混合物中的其它组分(Qa)的终点活性，单位为ppm；计算的SI值；以及各种被测组合的协同比范围(其它组分/MBlT或者A/B)。
表1
Ca：CYTO GUARD LA(月桂酰精氨酸乙酯盐酸盐)的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表2
Ca：MONTALINE C40(氯化(柯卡酰氨丙基-N-2-羟基乙基氨基甲酰基甲基二甲基铵))的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表3
Ca：ACQ D型(2-氨基乙醇铜(II)&氯化二癸基二甲基铵)的ppm AI(ppm CuO)
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表4
Ca：CARBOQUAT WP-50(碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵)的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表5
Ca：ACQ C2(2-氨基乙醇铜(II))的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表6
Ca：CAPMUL GML(单月桂酸甘油酯)的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表：7
Ca：CAPMUL PG12(单月桂酸丙二醇酯)的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb
表：8
Ca：Capmul PG8(辛酸丙二醇酯)的ppm AI
Cb：MBIT(N-甲基-1，2-苯并异噻唑啉-3-酮)的ppm AI
比例：Ca∶Cb

Claims (1)

1.一种杀微生物剂组合物，其包含以下组分:
(a)N-甲基-1,2-苯并异噻唑啉-3-酮；
(b)碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵，碳酸二癸基二甲基铵和碳酸氢二癸基二甲基铵与N-甲基-1,2-苯并异噻唑啉-3-酮之比为1:227至1:18.8或1:8.8471至1:0.5723。
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CN102308810A (zh) 2012-01-11
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EP2338339B1 (en) 2013-05-01
CN102308811A (zh) 2012-01-11
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BR122015027163B1 (pt) 2016-03-29
BR122015027160B1 (pt) 2016-03-29
CA2637129C (en) 2011-05-17

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