CN1492734A - 具有协同作用的杀生物组合物 - Google Patents
具有协同作用的杀生物组合物 Download PDFInfo
- Publication number
- CN1492734A CN1492734A CNA018145108A CN01814510A CN1492734A CN 1492734 A CN1492734 A CN 1492734A CN A018145108 A CNA018145108 A CN A018145108A CN 01814510 A CN01814510 A CN 01814510A CN 1492734 A CN1492734 A CN 1492734A
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- CN
- China
- Prior art keywords
- biocidal composition
- biocidal
- ketone
- znpy
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- Apparatus For Disinfection Or Sterilisation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及可以添加在可被有害微生物侵蚀的材料中的杀生物组合物,其含有2-巯基吡啶氧化物作为杀生物活性组分。该杀生物组合物的特征在于,其含有2-烷基异噻唑啉-3-酮作为另一种杀生物活性组分。该杀生物组合物的活性组分协同地发挥作用,并理想地适用于控制细菌、真菌和藻类。
Description
本发明涉及杀生物组合物作为能够被有害微生物攻击的物质的添加剂,它包括2-巯基吡啶氧化物作为杀生物活性组分。本发明特别涉及属于杀藻和杀真菌组合物的适合于防护工业物体和材料的杀生物组合物。
杀生物组合物被应用于许多领域,例如用于控制有害藻类、真菌和细菌。正如可以从US 5562995和JS 5883154中了解到的,大量的杀生物活性组分包括例如氧化2-巯基吡啶锌和氧化2-巯基吡啶钠。第一篇公开文献特别涉及如何避免在包括铁或铜离子以及2-巯基吡啶氧化物作为抗微生物活性组分的含水抗微生物混合物中发生不期望的脱色。通过添加锌离子可以避免脱色。第二篇公开文献特别涉及通过添加锌离子来防止或消除包含树脂、铁或铜离子和2-巯基吡啶氧化物的抗微生物混合物的不期望的脱色。
此外,包括氨基甲酸碘代炔丙酯作为杀生物活性组分的杀生物组合物已经描述在WO 96/39836中。
此外,还报导了2-正辛基异噻唑啉-3-酮的杀生物作用,根据EP-0676140-A1所述,可以将它例如作为与甲基异噻唑啉-3-酮的混合物使用。
另一种可商购的杀真菌剂是4,5-二氯-2-正辛基-4-异噻唑啉-3-酮,例如来自Rohm & Haas公司的“Rozone 2000”或来自Thor GmbH的“ACTICIDE”DT。
日本专利申请1992/353836中描述了包括1-氧化2-吡啶硫醇锌盐(即氧化2-巯基吡啶锌)和例如丁基氨基甲酸3-碘-2-丙炔基酯的杀微生物组合物。
此外,日本专利申请1993/99195中描述了经用于控制纺织纤维上真菌生长的组合物处理的纺织材料。这种组合物包含N-正丁基氨基甲酸的3-碘-2-丙炔基酯(即N-丁基氨基甲酸3-碘-2-丙炔基酯)和例如双(1-氧化2-吡啶基硫基)锌(即氧化2-巯基吡啶锌)。
此外,US 5464622中描述了包括2-巯基吡啶N-氧化物的锌盐(即氧化2-巯基吡啶锌)和丁基氨基甲酸碘代炔丙酯的杀微生物组合物。
最后,WO 98/21962涉及包括氧化2-巯基吡啶锌和卤代丙炔基化合物,例如丁基氨基甲酸3-碘-2-丙炔基酯的混合物的杀藻组合物。
现有技术中均没有涉及到除包括氧化2-巯基吡啶锌外还包括辛基异噻唑啉-3-酮的组合物。
包含上述其中一种杀生物活性组分的已知杀生物组合物对某些应用而言尚不能令人满意。正如经验所证实的,这尤其关系到其作为防腐剂赋予表面常受到藻类或真菌侵蚀的物体或涂料具有杀生物特性的用途。藻类或真菌的侵蚀不仅使得表面在外观上失去吸引力,而且还可以导致所述材料受到损坏并使所述物体和表面的使用寿命缩短。特别在湿度水平较高的场所可以发现微生物对场所中所应用的物体或涂料的侵蚀,所述场所既包括内部环境,例如食品工业建筑物如牛奶厂或酿酒厂的内部,又包括外部环境,尤其是接触不利气候条件的建筑物表面,例如缺乏日晒的建筑物表面。尤其是,包含上述杀生物活性组分之一的涂料表现出不能充分抵抗例如链格孢属种或其它来自称作“烟霉”的真菌组的真菌的定居。首先,微生物的生长导致外观受到损坏和与之相关的脱色。其次,当暴露在UV照射作用下时,多种杀生物活性组分倾向于脱色。
最后,一方面需要使用所述活性组分获得尽可能有效的杀生物作用,另一方面又必须仅使用相对少量的活性组分来达到这一目的。
由此本发明所基于的目的是指出因如下事实而得到改进的杀生物组合物,所述的事实即杀生物组合物的成分在上述工业材料和物体,特别是涂料系统,如油漆、清漆和打底用料(render)中以协同方式产生相互作用且由此为防止微生物侵蚀和破坏可以以比单独使用各成分时较低的浓度使用。优选所述的杀生物组合物应对细菌、真菌和藻类具有活性,特别是对霉菌、酵母、毁坏木材和使木材脱色的真菌以及藻类具有活性,此外还应在防污部份中对相关海洋生物、如Balus、海鞘(Ascidia)、龙介虫(Serpula)、贻贝(Mytilus)、螺旋虫(Spirorbis)、草苔虫(Bugula)和水螅虫(Hydrazoa)具有活性。在本文的上下文中,所述的杀生物组合物应表现出对链格孢属种和其它来自称作“烟霉”的真菌组的真菌具有活性,还应表现出对因UV光和高温作用而导致的脱色具有可能达到的最高程度的稳定性。
这一目的可以由本发明包括2-巯基吡啶氧化物(2-吡啶硫醇1-氧化物)作为杀生物活性组分的杀生物组合物来实现。该组合物的特征在于它包括2-烷基异噻唑啉-3-酮作为另一种杀生物活性组分。
本发明的杀生物组合物特别适合用作杀藻类和杀真菌组合物以保护对微生物侵蚀敏感的工业用材料。意图通过这种杀生物组合物进行保护以免受微生物改变或破坏的这类材料的实例是涂料系统,如颜料、清漆、打底用料(render)或防污漆,以及塑料、冷却润滑剂、传热流体、胶、胶料、纸和纸板、皮革、织物和木材。
定居在工业材料和上述类型物体上的微生物的实例以下列属为代表:
链格孢属(Alternaria),如链格孢(Alternaria alternata),
曲霉属(Aspergillus),如黑曲霉(Aspergillus niger),
短梗霉属(Aureobasidium),如出芽短梗霉(Aureobasidium pullulans),
毛壳属(Chaetomium),如球毛壳(Chaetomium globosum),
粉孢革菌属(Coniophora),如粉孢革菌(Coniophora puteana),
枝孢属(Cladosporium),如芽枝状枝孢(Cladosporiumcladosporoides),
假丝酵母属(Candida),如白假丝酵母(Candida albicans),
香菇属(Lentinus),如虎皮香菇(Lentinus tigrinus),
青霉属(Penicillium),如绳状青霉(Penicillium funiculosum),
红酵母属(Rhodotorula),如深红酵母(Rhodotorula rubra),
Sclerophoma,如Sclerophoma pityophila,
木霉属(Trichoderma),如绿色木霉(Trichoderma viride),
Ulocladium,如Ulocladium atrum,
埃希氏菌属(Escherichia),如大肠杆菌(Escherichia coli),
假单孢菌属(Pseudomonas),如铜绿假单孢菌(Pseudomonasaeruginosa),
葡萄球菌属(Staphylococcus),如白色葡萄球菌(Staphylococcusaureus)。
本发明特别适合用作涂料系统防腐剂的杀生物组合物具有下列积极特性:
a)良好的杀藻类作用;
b)良好的杀真菌作用;
c)在对抗链格孢属种和防腐领域中难以失活的其它问题微生物方面具有良好的活性,所述防腐领域尤其是指薄膜防腐和例如油漆(包括防污漆)、清漆和打底用料形式的涂料中的材料的防护以及木材、皮革和塑料的防护;
d)良好的持久性,甚至当处于强沥滤条件下和暴露于UV光、高温、极端天气条件和气候条件以及变化的天气条件时也是如此;
e)尽管使用低浓度的杀生物组合物,但是仍然具有长期的杀生物作用;
f)对人和哺乳动物具有低毒性;
g)所述杀生物活性组分的蒸汽压非常低;
h)有利的性/价比。
本发明杀生物组合物的出众之处在于2-巯基吡啶氧化物和2-烷基异噻唑啉-3-酮的混合物可以产生协同的杀生物作用。就需要良好的杀藻类作用而言,这使得例如可以不使用其它杀藻剂。
按照本发明,2-巯基吡啶氧化物优选以氧化2-巯基吡啶锌或氧化2-巯基吡啶钠的形式存在于所述的杀生物组合物中。然而,也可以使用氧化2-巯基吡啶铜和氧化2-巯基吡啶铁。所述的后面两种化合物表现出明显的内在颜色,由此仅适合于特定的应用,例如防污。
此外,有利的是,2-巯基吡啶氧化物以0.1-99.9%(重量)的浓度存在,而2-烷基异噻唑啉-3-酮(也可以是两种或多种2-烷基异噻唑啉-3-酮类化合物的混合物的形式)以0.1-99.9%(重量)的浓度存在,在每种情况中所述的重量百分比浓度均以整个杀生物组合物为基准。
在2-烷基异噻唑啉-3-酮中,烷基基团指的是正烷基、异烷基或新烷基。优选所述的烷基基团包含1-10、特别是1-8个碳原子。特别优选2-正辛基异噻唑啉-3-酮和4,5-二氯-2-正辛基异噻唑啉-3-酮。
本发明的杀生物组合物优选包含重量比为1∶1000-1000∶1、尤其是1∶99-99∶1、特别优选1∶10-10∶1、极为优选1∶3-3∶1的2-巯基吡啶氧化物与2-烷基异噻唑啉-3-酮。
已经显示出,使用2-巯基吡啶氧化物和2-烷基异噻唑啉-3-酮作为活性组分的本发明组合物在杀生物作用上的协同作用可以在该组合物另外还包括氨基甲酸碘代烷基酯、特别是N-丁基氨基甲酸3-碘-2-丙炔基酯作为补充的杀生物活性组分时得到进一步提高。
在一个具体的实施方案中,本发明的杀生物组合物除含有2-巯基吡啶氧化物和2-烷基异噻唑啉-3-酮外有意地不含有氨基甲酸碘代烷基酯。
有利的是在对微生物侵蚀敏感的系统中使用本发明组合物中的杀生物活性组分和极性或非极性的液体介质。在本文的上下文中,这种介质可以例如已经存在于所述的杀生物组合物中和/或待防护的系统中。
优选的极性液体介质是醇类、酯类、二元醇类、二元醇醚类、二元醇酯类和2,2,4-三甲基-1,3-戊二醇一异丁酸酯(在Eastman Chemical公司商品名为“Texanol”)。
优选的非极性液体介质是芳族化合物,如烷基苯类,例如二甲苯和甲苯;石蜡;非极性酯类,如邻苯二甲酸酯类和脂肪酸酯类;环氧化脂肪酸类及其衍生物;和硅油。
本发明的杀生物组合物优选具有4-10的pH、特别是6-8的pH。
上述杀生物活性组分,即2-巯基吡啶氧化物和氨基甲酸碘代烷基酯以及2-正辛基异噻唑啉-3-酮和/或4,5-二氯-2-正辛基异噻唑啉-3-酮,是已知的物质且可以通过现有技术的方法来制备,其中所述的2-巯基吡啶氧化物以例如氧化2-巯基吡啶锌、氧化2-巯基吡啶钠、氧化2-巯基吡啶铜和/或氧化2-巯基吡啶铁的形式存在,而氨基甲酸碘代烷基酯以例如N-丁基氨基甲酸3-碘-2-丙炔基酯、N-己基氨基甲酸3-碘-2-丙炔基酯、N-环己基氨基甲酸3-碘-2-丙炔基酯和/或N-苯基氨基甲酸3-碘-2-丙炔基酯的形式存在。
此外,本发明的杀生物组合物可以包括一种或多种其它杀生物活性组分,这些杀生物活性组分可以根据待防护的特定系统来选择。这类其它杀生物活性组分的实例如下所述:
三唑类化合物,如杀草强、三唑锡、BASF 480P、双苯三唑醇、噁醚唑、fenbuconazol、解草唑、fenethanil、氟喹唑、氟硅唑、粉唑醇、酰胺唑、isozofos、腈菌唑、叶菌唑、氟环唑、多效唑、戊菌唑、丙环唑、(±)-顺-1-(4-氯苯基)-2-(1H-1,2,4-三唑-1-基)环庚醇、氟醚唑、三唑酮、三唑醇、抑芽唑、氟菌唑、triconazole和烯效唑、及这些三唑类化合物的金属盐和酸加成物;
咪唑类化合物,如抑霉唑、稻瘟酯、唑鲜安、氟菌唑和2-(1-叔丁基)-1-(2-氯苯基)-3-(1,2,4-三唑-1-基)丙-2-醇,和这些咪唑类化合物的金属盐和酸加成物;
噻唑N-甲酰苯胺类化合物,如2’,6’-二溴-2-甲基-4-三氟甲氧基-4’-三氟甲基-1,3-噻唑-5-N-甲酰苯胺以及这些噻唑N-甲酰苯胺类化合物的金属盐和酸加成物;
(E)-2-{2-[6-(2-氰基苯氧基)嘧啶-4-基氧基]-苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2-硫代酰胺基苯氧基)嘧啶-4-基氧基]-苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2-氟苯氧基)嘧啶-4-基氧基]-苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2,6-二氟苯氧基)嘧啶-4-基氧基]-苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(嘧啶-2-基氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(5-甲基嘧啶-2-基氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(苯基磺酰基氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(4-硝基苯氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-(2-苯氧基)-3-甲氧基丙烯酸甲酯、(E)-2-[2-(3,5-二甲基苯甲酰基)吡咯-1-基]-3-甲氧基丙烯酸甲酯、(E)-2-[2-(3-甲氧基苯氧基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-[2-(2-苯基乙烯-1-基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-[2-(3,5-二氯苯氧基)吡啶-3-基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(1,1,2,2-四氟乙氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-α-羟基苄基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-[2-(4-苯氧基吡啶-2-基氧基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-[2-(3-正丙基氧基苯氧基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-[2-(3-异丙基氧基苯氧基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(2-氟苯氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-乙氧基苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-[2-(4-叔丁基吡啶-2-基氧基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(3-氰基苯氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-[2-(3-甲基吡啶-2-基氧基甲基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2-甲基苯氧基)嘧啶-4-基氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-[2-(5-溴吡啶-2-基氧基甲基)苯基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[3-(3-碘吡啶-2-基氧基)苯氧基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2-氯吡啶3-基氧基)嘧啶-4-基氧基]苯基}-3-甲氧基丙烯酸甲酯、(E,E)-2-[2-[5,6-二甲基吡嗪-2-基甲基肟基甲基]苯基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(6-甲基吡啶-2-基氧基)嘧啶-4-基氧基]苯基}-3-甲氧基丙烯酸甲酯、(E,E)-2-{2-[(3-甲氧基苯基)甲基肟基甲基]苯基]-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2-叠氮基苯氧基)嘧啶-4-基氧基]苯基}-3-甲氧基丙烯酸甲酯、(E,E)-2-{2-[6-(苯基嘧啶-4-基)甲基肟基甲基]苯基}-3-甲氧基丙烯酸甲酯、(E,E)-2-{2-[(4-氯苯基)甲基肟基甲基]苯基}-3-甲氧基丙烯酸甲酯、(E)-2-{2-[6-(2-正丙基苯氧基)-1,3,5-三嗪-4-基氧基]苯基}-3-甲氧基丙烯酸甲酯、(E,E)-2-{2-[(3-硝基苯基)甲基肟基甲基]苯基}-3-甲氧基丙烯酸甲酯;
琥珀酸脱氢酶抑制剂,如甲呋酰苯胺、二甲呋酰苯胺、环菌胺、拌种胺、Seedvax、噻菌胺、pyrocarbolid、氧化萎锈灵、防霉胺、邻酰胺(灭锈胺)、邻碘酰苯胺和氟酰胺(flutolanil,Moncut);
萘衍生物,如特比萘芬、萘替芬、布替萘芬、3-氯-7-(2-氮杂-2,7,7-三甲基辛-3-烯-5-炔);
次碘酰胺类化合物,如苯氟磺胺、甲苯氟磺胺、灭菌丹和fluorfolpet;
克菌丹、敌菌丹;
苯并咪唑类化合物,如多菌灵、苯菌灵、呋线威、麦穗宁、甲基硫菌灵和噻菌灵及它们的盐;
吗啉衍生物,如十三吗啉、丁苯吗啉、falimorph、烯酰吗啉、十二环吗啉、allimorph和苯锈啶,及其与芳基磺酸类化合物、例如与对甲苯磺酸和对十二烷基苯基磺酸形成的盐;
二硫代氨基甲酸盐类化合物,代森盐、福美铁、代森锰酮、代森锰锌、代森锰、威百亩、代森联、thiramzeneb、福美锌;
苯并噻唑类化合物,如2-巯基苯并噻唑;
苯甲酰胺类化合物,如2,6-二氯-N-(4-三氟甲基苄基)苯甲酰胺;
硼化合物,如硼酸、硼酸盐和硼砂;
甲醛和甲醛给体化合物,如苄醇一(聚)半缩甲醛、噁唑烷类化合物、六氢-S-三嗪类化合物、N-羟甲基氯乙酰胺、低聚甲醛、氯甲基吡啶(nitropyrine)、喹菌酮、叶枯酞;
双胍类化合物,如聚六亚甲基双胍;
三-N-(环己基二氮烯鎓二氧基)铝、N-(环己基二氮烯鎓二氧基)三丁基锡及其钾盐、双-N-(环己基二氮烯鎓二氧基)铜;
N-甲基异噻唑啉-3-酮、5-氯-N-甲基异噻唑啉-3-酮、4,5-三亚甲基异噻唑啉酮、1,2-苯并异噻唑啉酮、N-羟甲基氯乙酰胺;
醛类化合物,如肉桂醛、戊二醛和β-溴肉桂醛;
硫氰酸酯类化合物,如氰硫基甲基硫基苯并噻唑和亚甲基双硫氰酸酯;
季铵化合物,如氯化苄基二甲基十四烷基铵、氯化苄基二甲基十二烷基铵和氯化二癸基二甲基铵;
碘衍生物,如二碘甲基对甲苯基砜、3-碘-2-丙炔醇、二4-氯苯基-3-碘炔丙基甲醇缩甲醛、乙基氨基甲酸3-溴-2,3-二碘-2-丙烯基酯、2,3,3-三碘烯丙基醇、3-溴-2,3-二碘-2-丙烯基醇;
苯酚化合物,如三溴苯酚、四氯苯酚、3-甲基-3-氯苯酚、3,5-二甲基-4-氯苯酚、苯氧基乙醇、二氯芬、邻苯基苯酚、间苯基苯酚、对苯基苯酚和2-苄基-4-氯苯酚以及这些苯酚衍生物的碱金属和碱土金属盐;
含有活化的卤原子的杀微生物剂,如氯乙酰胺、溴代硝基丙二醇和bronodox;
Tectamers,如2-溴-2-硝基-1,3-丙二醇、2-溴-4’-羟基乙酰苯、2,2-二溴-3-腈丙酰胺、1,2-二溴-2,4-二氰基丁烷和β-溴-β-硝基苯乙烯;
四氯-4-甲基磺酰基吡啶、嘧霉胺(pyrimethanol)、嘧菌胺、吡菌硫;
金属皂,如环烷酸锡、环烷酸铜和环烷酸锌;辛酸锡、辛酸铜和辛酸锌;2-乙基己酸锡、2-乙基己酸铜和2-乙基己酸锌;油酸锡、油酸铜和油酸锌;磷酸锡、磷酸铜和磷酸锌;以及苯甲酸锡、苯甲酸铜和苯甲酸锌;
金属盐,如羟基碳酸铜、重铬酸钠、重铬酸钾、铬酸钾、硫酸铜、氯化铜、硼酸铜、氟硅酸锌、氟硅酸铜;
氧化物,如氧化三丁基锡、Cu2O、CuO、ZnO;
二烷基二硫代氨基甲酸盐,如二烷基二硫代氨基甲酸的钠盐和锌盐、二硫化四甲基秋兰姆和N-甲基二硫代氨基甲酸钾;
腈类化合物,如2,4,5,6-四氯间苯二氰、氰基二硫代亚氨基氨基甲酸二钠;
喹啉类化合物,如8-羟基喹啉及其铜盐;
粘氯酸、5-羟基-2-(5H)-呋喃酮;
4,5-二氯二噻唑啉酮、4,5-苯并二噻唑啉酮、4,5-三亚甲基二噻唑啉酮;
4,5-二氯-(3H)-1,2-二硫杂环戊烯-3-酮、3,5-二甲基四氢-1,3,5-噻二嗪-2-硫酮、氯化N-(2-对氯苯甲酰基乙基)六铵、N-羟甲基-N’-甲基二硫代氨基甲酸钾;
2-氧代-2-(4-羟基苯基)乙羟肟酰氯(acetohydroximinoyl chloride);
苯基2-氯氰基乙烯基砜、苯基1,2-二氯-2-氰基乙烯基砜;
单独或包封在聚合活性成分中的含有银、锌或铜的沸石;
杀藻剂,如硫酸铜、双氯酚、菌多杀、乙酸毒菌锡和灭藻醌;
除草剂,如乙草胺、三氟羧草醚、苯草醚、丙烯醛、甲草胺、禾草灭、莠灭净、酰醚磺隆、杀草强、硫酸铵、莎稗磷、磺草灵、莠去津、叠氮净、草除灵、乙丁氟灵、呋草黄、苄嘧黄隆、地散磷、benztazone、杀草敏、氟嘧黄隆、chloromethoxyfen、氯硝酚、一氯醋酸、氯化苦、绿麦隆、枯草隆、氯苯胺灵(chloroprepham)、绿黄隆、氯酞酸、草克乐、环庚草醚、醚黄隆、烯草酮、异噁草酮、稗草胺、二氯吡啶酸、氰氨化钙、氰草津、灭草特、噻草酮、吡草酮(benzofencap)、苯噻隆、甲羧除草醚、双丙氨酰膦、硼砂、除草定、溴丁酰草胺、溴酚肟、溴苯腈、丁草胺、抑草磷、丁烯草胺、双丁乐灵、丁草特、卡草胺、CGA 184927、灭草平、绿秀隆、稗蓼灵、正形素、枯莠隆、双苯唑快、吡氟草胺、丁噁隆、哌草丹、二草甲胺、二甲丙乙净、噻节因、二甲胂酸、氨基乙氟灵、地乐酚乙酸酯、地乐酚、特乐酚、双苯酰草胺、异丙净、敌草快、氟硫草定、敌草隆、DNOC、PPX-A788、2,4-D、杀草隆、茅草枯、棉隆、2,4-DB、甜菜安、敌草净、麦草畏、敌草腈、2,4-滴丙酸、高2,4-滴丙酸盐、禾草灵、乙酰甲草胺、麦草伏M、啶嘧黄隆、fluazifop、吡氟禾草灵、环丙氟灵、伏草隆、乙羧氟草醚、氟化除草醚、四氟丙酸、芴丁酸、氟定酮、氟咯草酮、氟草烟、氟黄胺草醚、fusamin、氟呋草醚、草胺膦、草甘膦、吡氟氯禾灵、环嗪酮、醚草酯、灭草烟、灭草喹、咪草烟、碘苯腈、异丙乐灵、异丙隆、异噁隆、isoxaben、噁草醚、乳氟禾草灵、环草定、利谷隆、LS830556、MCPA、克草猛、二甲戊乐灵、五氯代酚、戊酰苯草胺、矿油馏份、甜菜宁、毒莠定、哌草磷、丙草胺、氟嘧黄隆、氨基丙氟灵、甘扑津、扑灭通、扑草净、毒草胺、敌稗、喔草酯、扑灭津、苯胺灵、戊炔草胺、苄草丹、吡唑特、吡嘧黄隆、苄草唑、稗草畏、哒草特、二氯喹啉酸、喹草酸、灭藻醌、quizalofop、喹禾灵、S-23121、DPX-E96361、DSMA、甘草津、茵多杀、epsorcarb、EPTC、乙丁烯氯灵、赛黄隆、乙呋草黄、噁唑禾草灵、高噁唑禾草灵、非草隆、麦草伏、irgarol 1051、硫代乙基-MCPA、MCPB、2甲4氯丙酸、2甲4氯丙酸盐、苯噻草胺、伏草胺、威百亩、苯嗪草酮、吡草胺、甲基苯噻隆、灭杀唑、甲氧丙净、甲基杀草隆、异硫氰酸甲酯、秀谷隆、异丙甲草胺、甲氧隆、嗪草酮、甲黄隆、草达灭、庚草利、绿谷隆、MSMA、萘丙胺、萘氧丙草胺、萘草胺、草不隆、咽嘧黄隆、吡氯草胺、哒草伏、坪草丹、安磺灵、噁草酮、乙氧氟草醚、百草枯、扑草净、西草净、SMY 1500、氯酸钠、嘧黄隆、重焦油、TCA、牧草胺、特丁噻草隆、特草定、特丁通、特丁津、特丁净、噻氟隆、噻黄隆、杀草丹、thiocarbazil、嘧草胺、肟草酮、野燕畏、醚苯黄隆、苯黄隆、绿草定、灭草环、草达津、氟乐灵、UB1-C4874、灭草猛。
本发明的杀生物组合物可以进一步包括对杀生物剂领域的普通技术人员而言已知作为添加剂的常用成分。它们的实例有增稠剂、消泡剂、pH调节剂、香料、分散剂和稳定剂如缓冲剂、锌盐、氧化锌和络合剂。
当实际应用时,可以以备好的混合物的形式或通过向易受微生物侵蚀并有待防护的系统中分开添加组合物中的杀生物剂和剩余成分来引入杀生物组合物。一般地,就例如颜料、打底用料、塑料和皮革的情况而言,在对微生物侵蚀敏感并有待防护的系统中杀生物剂的总浓度为0.01-10%。如果将所述的杀生物剂用作防污活性组分,那么它们在待防护的系统中的总浓度为0.1-50%。就木材防护中应用杀生物剂的情况而言,通常以0.1-20%的总浓度使用它们。在每种情况中,这些浓度是就待防护系统和杀生物组合物的完整混合物而言的。
如下实施例举例说明本发明。
实施例1
本实施例证实了在本发明杀生物组合物中氧化2-巯基吡啶锌(ZnPy)、N-丁基氨基甲酸3-碘-2-丙炔基酯(IPBC)和2-正辛基异噻唑啉-3-酮(OIT)组合的协同作用。
为了该目的,制备具有一方面是不同浓度的ZnPy和OIT混合物(重量比80∶20)而另一方面是不同浓度的N-丁基氨基甲酸3-碘-2-丙炔基酯(IPBC)的含水混合物并测试这些混合物对绳状青霉DSM 12637的作用。
除所述的杀生物剂成分和水外,所述的含水混合物还包含营养培养基,即沙氏麦芽糖肉汤(商品,Merck No.10393)。细胞密度为106个细胞/ml。孵育时间在25℃下为96小时。以120rpm在摇床-孵育箱中孵育每一样品。
下文表I显示了一方面ZnPy和OIT的混合物的浓度及另一方面IPBC的浓度。从该表中还可以看出微生物的生长是发生(符号“+”)还是没有发生(符号“-”)。
因此,表I也显示了最低抑制浓度(MIC)。由此,当仅使用ZnPy和OIT的混合物(重量比80∶20)时,MIC值为0.75ppm,而当仅使用IPBC时,MIC值为2ppm。相比之下,具有一方面是ZnPy+OIT而另一方面是IPBC的混合物的MIC值明显较低,也就是说,联合的这些混合物协同地发挥作用。
表I
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy/OIT(80∶20)+IPBC的MIC值
ZnPy/OIT(80∶20)浓度(ppm) | IPBC浓度(ppm)3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0.05 0 |
53.0210.750.50.40.30.20.10.050 | - - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - + +- - - - + + + + + + +- - - - + + + + + + +- - - - + + + + + + +- - - + + + + + + + +- - + + + + + + + + + |
使用表II中所示的协同作用指数计算,以数字形式表示存在的协同作用。通过F.C.Kull等在《应用微生物学》(Applied Microbiology),第9卷(1961),p538中所述的方法来计算所述的协同作用指数。这里,我们使用下列公式计算协同作用指数:
协同作用指数SI=Qa/QA+Qb/QB。
当将该公式应用于本上下文中测试的杀生物剂系统时,公式中的参数具有下列含义:
Qa=ZnPy/IPBC杀生物剂混合物中ZnPy的浓度
QA=ZnPy作为唯一杀生物剂时的浓度
Qb=ZnPy/IPBC杀生物剂混合物中IPBC的浓度
QB=IPBC作为唯一杀生物剂时的浓度
如果协同作用指数的值大于1,那么这意味着存在拮抗作用。如果协同作用指数的值表现为1,那么这意味着存在两种杀生物剂的加和作用。如果协同作用指数的值表现为小于1,那么这意味着存在两种杀生物剂的协同作用。
当一方面使用ZnPy/OIT(重量比80∶20)、而另一方面又同时使用IPBC时,存在协同作用。可以从表II中观察到协同作用指数的计算。因此,就绳状青霉DSM 12637而言,发现11.8%(重量)的ZnPy/OIT(80∶20)和88.2%(重量)的IPBC的混合物具有最低的协同作用指数(0.58)。
表II
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy/OIT(80∶20)+IPBC的协同作用指数的计算
MIC值当 | ZnPy/OIT+IPBC的总浓度Qa+Qb(ppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy/OIT(80∶20)浓度Qa(ppm) | IPBC浓度Qb(ppm) | ZnPy/OIT(80∶20)(重量%) | IPBC(重量%) | ||||
00.050.10.20.40.5 | 210.750.750.10 | 21.050.850.950.50.5 | 0.04.811.821.180.0100.0 | 100.095.288.278.920.00.0 | 0.000.100.200.400.801.00 | 1.000.500.380.380.050.00 | 1.000.600.580.780.851.00 |
实施例2
按照与实施例1类似的方式证实了ZnPy、IPBC和4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(DCOIT)的混合物对微生物绳状青霉DSM 12637的协同作用。在每种情况中,ZnPy与DCOIT的重量比均为80∶20。
再次,各批实验中均包含沙氏麦芽糖肉汤作为营养培养基。细胞密度为106个细胞/ml。孵育时间在25℃下为96小时。以120rpm在摇床-孵育箱中孵育每一样品。
从如下的表III中可以观察到所测试的杀生物组合物的MIC值。当仅使用ZnPy/DCOIT混合物(重量比80∶20)时,MIC值为0.50ppm,而当仅使用IPBC时,MIC值为2ppm。
表III
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy/DCOIT(80∶20)+IPBC的MIC值
ZnPy/DCOIT(80∶20)浓度(ppm) | IPBC浓度(ppm)3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0.05 0 |
53.0210.750.50.40.30.20.10.050 | - - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - - - +- - - - - - - - - - +- - - - - - - - + + +- - - - + + + + + + +- - - + + + + + + + +- - + + + + + + + + + |
当一方面使用ZnPy/DCOIT(重量比80∶20)、而另一方面又同时使用IPBC时,存在协同作用。可以从表IV中观察到协同作用指数的计算。由此,就绳状青霉DSM 12637而言,发现50.0%(重量)的ZnPy/DCOIT(80∶20)和50.0%(重量)的IPBC的混合物具有最低的协同作用指数(0.50)。
表IV
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy/DCOIT(80∶20)+IPBC的协同作用指数的计算
此时的MIC | ZnPY/DCOIT+IPBC的总浓度Qa+Qb(ppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy/DCOIT(80∶20)浓度Qa(ppm) | IPBC浓度Qb(ppm) | ZnPy/DCOIT(80∶20)(重量%) | IPBC(重量%) | ||||
00.050.10.20.20.20.30.30.40.5 | 210.750.40.30.20.10.050.050 | 21.050.850.60.50.40.40.350.450.5 | 0.04.811.833.340.050.075.085.788.9100.0 | 100.095.288.266.760.050.025.014.311.10.0 | 0.000.100.200.400.400.400.600.600.801.00 | 1.000.500.200.150.100.050.030.030.000.00 | 1.000.600.580.600.550.500.650.630.831.00 |
实施例3
按照与实施例1类似的方式证实了ZnPy和OIT对微生物绳状青霉DSM 12637的协同作用。
再次,各批实验中均包含沙氏麦芽糖肉汤作为营养培养基。细胞密度为106个细胞/ml。孵育时间在25℃下为96小时。以120rpm在摇床-孵育箱中孵育每一样品。
从如下的表V中可以观察到所测试的杀生物组合物的MIC值。当仅使用ZnPy时,MIC值为2ppm,而当仅使用OIT时,MIC值为0.5ppm。
表V
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy+OIT的MIC值
ZnPy浓度(ppm) | OIT浓度(ppm)3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0 |
53.0210.750.50.40.30.20.10 | - - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - +- - - - - - - - - +- - - - - - - - + +- - - - - - - - + +- - - - - - - + + +- - - - - - + + + +- - - - - + + + + +- - - - - + + + + + |
当同时使用ZnPy和OIT时,存在协同作用。可以从表VI中观察到协同作用指数的计算。由此,就绳状青霉DSM 12637而言,发现88.2%(重量)的ZnPy和11.8%(重量)的OIT的混合物具有最低的协同作用指数(0.58)。
表VI
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy+OIT的协同作用指数的计算
MIC值当 | ZnPY+OIT的总浓度Qa+Qb(ppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy浓度Qa(ppm) | OIT浓度Qb(ppm) | ZnPy(重量%) | OIT(重量%) | ||||
00.20.30.40.50.7512 | 0.50.40.30.20.20.10.10 | 0.50.60.60.60.70.851.12 | 0.033.350.066.771.488.290.9100.0 | 100.066.750.033.328.611.89.10.0 | 0.000.100.150.200.250.380.501.00 | 1.000.800.600.400.400.200.200.00 | 1.000.900.750.600.650.580.701.00 |
实施例4
按照与实施例1类似的方式证实了ZnPy和OIT对微生物绳状青霉IMI 211742的协同作用。
再次,各批实验中均包含沙氏麦芽糖肉汤作为营养培养基。细胞密度为106个细胞/ml。孵育时间在25℃下为72小时。以120rpm在摇床-孵育箱中孵育每一样品。
从如下的表VII中可以观察到所测试的杀生物组合物的MIC值。当仅使用ZnPy时,MIC值为1ppm,而当仅使用IPBC时,MIC值为0.75ppm。
表VII
绳状青霉IMI 211742:在72小时/25℃的孵育时间下
ZnPy+OIT的MIC值
ZnPy浓度(ppm) | OIT浓度(ppm)3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0 |
53.0210.750.50.40.30.20.10 | - - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - +- - - - - - - - - +- - - - - - - + + +- - - - - - + + + +- - - - + + + + + +- - - - + + + + + +- - - - + + + + + + |
当同时使用ZnPy和OIT时,存在协同作用。可以从表VIII中观察到协同作用指数的计算。由此,就绳状青霉IMI 211742而言,发现83.3%(重量)的ZnPy和16.7%(重量)的OIT的混合物具有最低的协同作用指数(0.63)。
表VIII
绳状青霉IMI 211742:在72小时/25℃的孵育时间下
ZnPy+OIT的协同作用指数的计算
MIC值当 | ZnPY+OIT的总浓度Qa+Qb(ppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy浓度Qa(ppm) | OIT浓度Qb(ppm) | ZnPy(重量%) | OIT(重量%) | ||||
00.30.30.40.50.50.751 | 0.750.50.40.30.20.10.10 | 0.750.80.70.70.70.60.851 | 0.037.542.957.171.483.388.2100.3 | 100.062.557.142.928.616.711.80.0 | 0.000.300.300.400.500.500.751.00 | 1.000.670.530.400.270.130.130.00 | 1.000.970.830.800.770.630.881.00 |
实施例5
按照与实施例1类似的方式证实了ZnPy和DCOIT对微生物绳状青霉DSM 12637的协同作用。
再次,各批实验中均包含沙氏麦芽糖肉汤作为营养培养基。细胞密度为106个细胞/ml。孵育时间在25℃下为96小时。以120rpm在摇床-孵育箱中孵育每一样品。
从如下的表IX中可以观察到所测试的杀生物组合物的MIC值。当仅使用ZnPy时,MIC值为2ppm,而当仅使用DCOIT时,MIC值为2ppm。
表IX
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy+DCOIT的MIC值
ZnPy浓度(ppm) | DCOIT浓度(ppm)3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0 |
53.0210.750.50.40.30.20.10 | - - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - +- - - - - - - - - +- - - - - - - - + +- - - - - - - + + +- - - - - + + + + +- - - + + + + + + +- - + + + + + + + +- - + + + + + + + + |
当同时使用ZnPy和DCOIT时,存在协同作用。可以从表X中观察到协同作用指数的计算。由此,就绳状青霉DSM 12637而言,发现57.1%-71%(重量)的ZnPy和42.9%-28.6%(重量)的DCOIT的混合物具有最低的协同作用指数(0.35)。
表X
绳状青霉DSM 12637:在96小时/25℃的孵育时间下
ZnPy+DCOIT的协同作用指数的计算
MIC值当 | ZnPY+DCOIT总浓度Qa+Qb(ppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy浓度Qa(ppm) | DCOIT浓度Qb(ppm) | ZnPy(重量%) | DCOIT(重量%) | ||||
00.20.30.30.40.40.50.7512 | 210.750.50.40.30.20.10.10 | 21.21.050.80.80.70.70.851.12 | 0.016.728.637.550.057.171.488.290.9100.0 | 100.083.371.462.550.042.928.611.89.10.0 | 0.000.100.150.150.200.200.250.380.501.00 | 1.000.500.380.250.200.150.100.050.050.00 | 1.000.600.530.400.400.350.350.430.551.00 |
实施例6
按照与实施例1类似的方式证实了ZnPy和DCOIT对微生物绳状青霉IMI 211742的协同作用。
再次,各批实验中均包含沙氏麦芽糖肉汤作为营养培养基。细胞密度为106个细胞/ml。孵育时间在25℃下为72小时。以120rpm在摇床-孵育箱中孵育每一样品。
从如下的表XI中可以观察到所测试的杀生物组合物的MIC值。当仅使用ZnPy时,MIC值为0.75ppm,而当仅使用DCOIT时,MIC值为1ppm。
表XI
绳状青霉IMI 211742:在72小时/25℃的孵育时间下
ZnPy+DCOIT的MIC值
ZnPy浓度(ppm) | DCOIT浓度(ppm)3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0 |
53.0210.750.50.40.30.20.10 | - - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - + +- - - - - - - - + +- - - - - - + + + +- - - - - + + + + +- - - - + + + + + +- - - + + + + + + + |
当同时使用ZnPy和DCOIT时,存在协同作用。可以从表XII中观察到协同作用指数的计算。由此,就绳状青霉IMI 211742而言,发现66.7%(重量)的ZnPy和33.3%(重量)的DCOIT的混合物具有最低的协同作用指数(0.73)。
表XII
绳状青霉IMI 211742:在72小时/25℃的孵育时间下
ZnPy+DCOIT的协同作用指数的计算
MIC值当 | ZnPY+DCOIT总浓度Qa+Qb(ppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy浓度Qa(ppm) | DCOIT浓度Qbppm) | ZnPy(重量%) | DCOIT(重量%) | ||||
00.10.20.30.40.40.50.75 | 10.750.50.40.30.20.20 | 10.850.70.70.70.60.70.75 | 0.011.828.642.957.166.771.4100.0 | 100.088.271.457.142.933.328.60.0 | 0.000.130.270.400.530.530.671.00 | 1.000.750.500.400.300.200.200.00 | 1.000.880.770.800.830.730.871.00 |
实施例7
按照与实施例1类似的方式证实了ZnPy和DCOIT对微生物黑曲霉DSM 1957的协同作用。
再次,各批实验中均包含沙氏麦芽糖肉汤作为营养培养基。细胞密度为106个细胞/ml。孵育时间在25℃下为72小时。以120rpm在摇床-孵育箱中孵育每一样品。
从如下的表XIII中可以观察到所测试的杀生物组合物的MIC值。当仅使用ZnPy时,MIC值为17.5ppm,而当仅使用DCOIT时,MIC值为0.75ppm。
表XIII
黑曲霉DSM 1957:在72小时/25℃的孵育时间下
ZnPy+DCOIT的MIC值
ZnPy浓度(ppm) | IPBC浓度(ppm)5 4 3 2 1 0.75 0.5 0.4 0.3 0.2 0.1 0 |
2017.515.012.5107.5543210 | - - - - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - + + +- - - - - - - - - + + +- - - - - - - - - + + +- - - - - - - - - + + +- - - - - - - - - + + +- - - - - - - + + + + +- - - - - - - + + + + +- - - - - - - + + + + +- - - - - - - + + + + +- - - - - - + + + + + + |
当同时使用ZnPy和DCOIT时,存在协同作用。可以从表XIV中观察到协同作用指数的计算。由此,就黑曲霉DSM 1957而言,发现94.3%(重量)的ZnPy和5.7%(重量)的DCOIT的混合物具有最低的协同作用指数(0.69)。
表XIV
黑曲霉DSM 1957:在72小时/25℃的孵育时间下
ZnPy+DCOIT的协同作用指数的计算
MIC值当 | ZnPY+DCOIT总浓度Qa+Qbppm) | 浓度 | Qa/QA | Qb/QB | 协同作用指数Qa/QA+Qb/QB | ||
ZnPy浓度Qa(ppm) | DCOIT浓度Qbppm) | ZnPy(重量%) | DCOIT(重量%) | ||||
01234557.51017.5 | 0.750.50.50.50.50.40.30.30.30 | 0.751.52.53.54.55.45.37.810.317.5 | 0.066.780.085.788.992.694.396.297.1100.0 | 100.033.320.014.311.17.45.73.82.90.0 | 0.000.060.110.170.230.290.290.430.571.00 | 1.000.670.670.670.670.530.400.400.400.00 | 1.000.720.780.840.900.820.690.830.971.00 |
实施例8-13
为了测试涂料的杀真菌和杀藻薄膜防护作用,在这些材料的样品中添加不同浓度的杀生物剂并使用刷子或刮铲将它们涂在适宜的支持物材料上,例如将这些样品涂在约5cm×5cm大小的硅酸钙片状物上。涂层在20±1℃下干燥后,使它们在规定期限中接触水。
当测试杀真菌防护作用时,将已经接触了水或没有接触水的测试物体包埋在琼脂营养培养基中,所述的营养培养基不覆盖该样品表面。随后给包埋的测试物体喷洒符合实际条件的真菌的孢子悬浮液然后存放在对真菌而言最佳的生长条件下。
为了测试杀藻防护作用,将已经接触了水或没有接触水的测试物体置于含有所选择的藻类的特定藻类用营养溶液中,其中所选择的藻类是与实际条件相符的,然后将测试物体存放在对藻类而言最佳的生长条件下。在相应存放后,评价测试物体表面上真菌或藻类生长的程度。
在测试杀真菌防护作用中,使用有代表性的下列物种的等份孢子混合物:
链格孢
黑曲霉
芽枝状枝孢
绳状青霉
Ulocladium atrum
关键词:
o=没有观察到生长
x=极低程度的生长(覆盖达25%的区域)
xx=轻度生长(覆盖达50%的区域)
xxx=中度生长(覆盖达75%的区域)
xxxx=大量生长(覆盖达100%的区域)
在实施例8-10中,测试具有如下表XV中所示组成的无光泽外用漆的杀真菌和杀藻防护作用。
表XV
外用漆
成分
按重量计的份数
水 65
Pigmentverteiler A(BASF AG) 3
多磷酸钠,25%浓溶液 4
浓缩氨(ammoniak) 2
防腐剂ACTICIDEFI(Thor GmbH) 3
2%甲基纤维素浓溶液,20 000mPas 100
石油溶剂(180-210℃) 13
LusolvanFBH(BASF AG) 7
LumitenN-OC30(BASF AG) 10
金红石型二氧化钛,Kronos2043 180
(Kronos-Titan GmbH)
Omvacarb5GU(Omya GmbH) 240
滑石,5μm 50
消泡剂Agitan280(Münzing Chemie GmbH) 3
聚丙烯酸酯Acronal290D(BASF AG)
320
1000
在实施例11-13中,测试具有如下表XVI中所示组成的抹光打底用料(float-finish rendering)的杀真菌和杀藻防护作用:
表XVI
抹光打底用料
成分
按重量计的份数
25%多磷酸钠浓溶液 8
防腐剂ACTICIDEFI(Thor GmbH) 3
消泡剂Agitan280(Münzig Chemie GmbH) 3
聚丙烯酸酯LatekollD,8%氨溶液(BASF AG) 8
石油溶剂(180-210℃) 10
丁基二甘醇醚 10
BasophobWDS(BASF AG) 6
金红石型二氧化钛,Kronos2044 28
(Kronos-Titan GmbH)
Omyacarb40GU(Omya GmbH) 395
Omyacarb130GU(Omya GmbH) 255
Plastorit(Luzenac Deutschland GnbH) 65
石英颗粒 45
水 32
Acronal 290D
132
1000
实施例8
测试上述外用漆薄膜的防护特性。
所用的杀生物组合物是如下的含水杀生物组合物I。所述百分数是基于外用漆和活性组分的整个含水混合物的百分数。
杀生物组合物I:
ZnPy 3%
IPBC 2%
OIT 3%
下表XVII显示了实验中使用的活性组分的量、使杀生物剂所防护的薄膜接触水的时间和实验结束时薄膜表面上真菌和藻类的生长情况。
表XVII
使用杀生物组合物I时上述外用漆薄膜对真菌和藻类生长的防护作用
序号 | 活性组分ZnPY/IPBC/OIT的用量(ppm) | 接触水(天) | 薄膜表面上的真菌生长 | 薄膜表面上的藻类生长 |
1234567891011121314 | 30/20/3030/20/3060/40/6060/40/6090/60/9090/60/90150/100/150150/100/150225/150/225225/150/225300/200/300300/200/3000/0/0 (比较)0/0/0 (比较) | 02020202020202 | xxxxxxxxx000000xxxxxx | xxxxxxxxxxxxx0xxx0xxx0xx00xxxxxxxx |
实施例9
重复实施例8,但是使用如下的含水杀生物组合物II。所述的百分数是以外用漆和活性组分的整个含水混合物为基准的百分数。
杀生物组合物II:
ZnPy 3%
IPBC 2%
DCOIT 3%
下表XVIII显示了实验中所用活性组分的量、使杀生物剂所防护的薄膜接触水的时间和实验结束时薄膜表面上真菌和藻类的生长情况。
表XVIII
使用杀生物组合物II时上述外用漆薄膜对真菌和藻类生长的防护作用
序号 | 活性组分ZnPY/IPBC/DCOIT的用量(ppm) | 接触水(天) | 薄膜表面上的真菌生长 | 薄膜表面上的藻类生长 |
1234567891011121314 | 30/20/3030/20/3060/40/6060/40/6090/60/9090/60/90150/100/150150/100/150225/150/225225/150/225300/200/300300/200/3000/0/0 (比较)0/0/0 (比较) | 02020202020202 | xxxxxxx00000000xxxxxx | xxxxxxxxxxxxxxxxxxxxxxxxx0xx00xxxxxxxx |
实施例10
重复实施例8,但是使用如下的含水杀生物组合物III。所述的百分数是以外用漆和活性组分的整个含水混合物为基准的百分数。
杀生物组合物III:
ZnPy 3%
IPBC 2%
OIT 1.5%
DCOIT 1.5%
下表IX显示了实验中所用活性组分的量、使杀生物剂所防护的薄膜接触水的时间和实验结束时薄膜表面上真菌和藻类的生长情况。
表XIX
使用杀生物组合物III时上述外用漆薄膜对真菌和藻类生长的防护作用
序号 | 活性组分ZnPY/IPBC/OIT/DCOIT的用量(ppm) | 接触水(天) | 薄膜表面上的真菌生长 | 薄膜表面上的藻类生长 |
1234567891011121314 | 30/20/15/1530/20/15/1560/40/30/3060/40/30/3090/60/45/4590/60/45/45150/100/75/75150/100/75/75225/150/112.5/112.5225/150/112.5/112.5300/200/150/150300/200/150/1500/0/0 (比较)0/0/0 (比较) | 02020202020202 | xxxxxx00000000xxxxxx | xxxxxxxxxxxx0xx0x0000xxxxxxxx |
实施例11
重复实施例8,但是使用上述抹光打底用料代替外用漆。
结果汇集在下面的表XX中。
表XX
使用杀生物组合物I时上述抹光打底用料薄膜
对真菌和藻类生长的防护作用
序号 | 活性组分ZnPY/IPBC/OIT的用量(ppm) | 接触水(天) | 薄膜表面上的真菌生长 | 薄膜表面上的藻类生长 |
123456789101112 | 30/20/3030/20/3060/40/6060/40/6090/60/9090/60/90150/100/150150/100/150225/150/225225/150/2250/0/0 (比较)0/0/0 (比较) | 020202020202 | 0000000000xxxxxx | 0xxxx00000000xxxxxxxx |
实施例12
重复实施例11,但是使用含水杀生物组合物II。
结果汇集在下面的表XXI中。
表XXI
使用杀生物组合物II时上述抹光打底用料薄膜
对真菌和藻类生长的防护作用
序号 | 活性组分ZnPY/IPBC/DCOIT的用量(ppm) | 接触水(天) | 薄膜表面上的真菌生长 | 薄膜表面上的藻类生长 |
123456789101112 | 30/20/3030/20/3060/40/6060/40/6090/60/9090/60/90150/100/150150/100/150225/150/225225/150/2250/0/0 (比较)0/0/0 (比较) | 020202020202 | xxxx000000xxxxxx | 0xxx0x000000xxxxxxxx |
实施例13
重复实施例11,但使用含水的杀生物组合物III。
结果汇集在下面的表XXII中。
表XXII
使用杀生物组合物III时上述抹光打底用料薄膜
对真菌和藻类生长的防护作用
序号 | 活性组分ZnPY/IPBC/OIT/DCOIT的用量(ppm) | 接触水(天) | 薄膜表面上的真菌生长 | 薄膜表面上的藻类生长 |
123456789101112 | 30/20/15/1530/20/15/1560/40/30/3060/40/30/3090/60/45/4590/60/45/45150/100/75/75150/100/75/75225/150/112.5/112.5225/150/112.5/112.50/0/0 (比较)0/0/0 (比较) | 020202020202 | xxxxx00000000xxxxxx | xxxxxxx00000000xxxxxxxx |
Claims (14)
1.作为能够被有害微生物侵蚀的物质的添加剂且包含2-巯基吡啶氧化物作为杀生物活性组分的杀生物组合物,其特征在于该杀生物组合物包含2-烷基异噻唑啉-3-酮作为另一种杀生物活性组分。
2.如权利要求1中所述的杀生物组合物,其特征在于所含的2-巯基吡啶氧化物是氧化2-巯基吡啶锌、氧化2-巯基吡啶钠、氧化2-巯基吡啶铜和/或氧化2-巯基吡啶铁。
3.如权利要求1或2中所述的杀生物组合物,其特征在于2-巯基吡啶氧化物的存在浓度为整个杀生物组合物的0.5-99.5%重量。
4.如权利要求1-3中任意一项所述的杀生物组合物,其特征在于2-烷基异噻唑啉-3-酮的存在浓度为整个杀生物组合物的0.1-99.9%重量。
5.如权利要求1-4中任意一项所述的杀生物组合物,其特征在于所述的2-烷基异噻唑啉-3-酮是2-正辛基异噻唑啉-3-酮或4,5-二氯-2-正辛基异噻唑啉-3-酮或这两种化合物的混合物。
6.如权利要求1-5中任意一项所述的杀生物组合物,其特征在于所述2-巯基吡啶氧化物与所述2-烷基异噻唑啉-3-酮以1∶1000-1000∶1的重量比存在。
7.如权利要求6中所述的杀生物组合物,其特征在于所述2-巯基吡啶氧化物与所述2-正辛基异噻唑啉-3-酮和/或4,5-二氯-2-正辛基异噻唑啉-3-酮以1∶10-10∶1的重量比存在。
8.如权利要求1-7中任意一项所述的杀生物组合物,其特征在于所述2-巯基吡啶氧化物和所述2-烷基异噻唑啉-3-酮以占整个杀生物组合物的0.2-100%重量的总浓度存在。
9.如权利要求1-8中任意一项所述的杀生物组合物,其特征在于不存在氨基甲酸碘代烷基酯。
10.如权利要求1-8中任意一项所述的杀生物组合物,其特征在于氨基甲酸碘代烷基酯作为补充的杀生物活性组分存在。
11.如权利要求10中所述的杀生物组合物,其特征在于所含的氨基甲酸碘代烷基酯是N-丁基氨基甲酸3-碘-2-丙炔基酯。
12.如权利要求1-11中任意一项所述的杀生物组合物在控制易受微生物侵蚀的系统中的有害微生物中的用途。
13.如权利要求12中所述的用途,其特征在于所述的杀生物组合物被用于保护涂料、皮革、塑料或木材。
14.对有害微生物有防腐作用的物质混合物或材料,其特征在于内含有如权利要求1-11中任意一项所述的杀生物组合物。
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2001
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- 2001-08-20 AU AU2001291778A patent/AU2001291778A1/en not_active Abandoned
- 2001-08-20 RU RU2003107681/04A patent/RU2278515C2/ru not_active IP Right Cessation
- 2001-08-20 CN CNB018145108A patent/CN1287667C/zh not_active Expired - Fee Related
- 2001-08-20 JP JP2002520620A patent/JP2004524263A/ja active Pending
- 2001-08-20 DE DE50109633T patent/DE50109633D1/de not_active Expired - Lifetime
- 2001-08-20 AT AT01971931T patent/ATE324040T1/de active
- 2001-08-20 EP EP01971931A patent/EP1313368B1/de not_active Revoked
- 2001-08-20 PT PT06005869T patent/PT1671542E/pt unknown
- 2001-08-20 AT AT06005869T patent/ATE410923T1/de active
- 2001-08-20 BR BRPI0113384-5A patent/BRPI0113384B1/pt not_active IP Right Cessation
- 2001-08-20 EP EP06005869A patent/EP1671542B1/de not_active Revoked
- 2001-08-20 EP EP20080162324 patent/EP2033519A1/de not_active Withdrawn
- 2001-08-20 DE DE50114436T patent/DE50114436D1/de not_active Expired - Lifetime
- 2001-08-20 ES ES06005869T patent/ES2314769T3/es not_active Expired - Lifetime
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- 2001-08-20 CZ CZ2003509A patent/CZ2003509A3/cs unknown
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102613238A (zh) * | 2010-12-22 | 2012-08-01 | 陶氏环球技术有限公司 | 草甘膦化合物和dcoit或oit或bbit中一种的协同组合 |
CN102613238B (zh) * | 2010-12-22 | 2016-02-10 | 陶氏环球技术有限公司 | 草甘膦化合物和dcoit或oit或bbit中一种的协同组合 |
CN105188377A (zh) * | 2013-03-28 | 2015-12-23 | 陶氏环球技术有限责任公司 | 绿麦隆和辛基异噻唑啉酮(oit)的协同组合用于干膜保护 |
CN105188377B (zh) * | 2013-03-28 | 2017-09-01 | 陶氏环球技术有限责任公司 | 绿麦隆和辛基异噻唑啉酮(oit)的协同组合用于干膜保护 |
CN113292553A (zh) * | 2021-05-12 | 2021-08-24 | 烟台大学 | 中肋骨条藻杀藻用芳基噻唑-色胺类化合物及其组合剂 |
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DE10040814A1 (de) | 2002-03-07 |
EP1313368B1 (de) | 2006-04-26 |
WO2002015693A1 (de) | 2002-02-28 |
BR0113384A (pt) | 2003-07-29 |
DE50109633D1 (de) | 2006-06-01 |
US6846777B2 (en) | 2005-01-25 |
ATE324040T1 (de) | 2006-05-15 |
ATE410923T1 (de) | 2008-10-15 |
JP2004524263A (ja) | 2004-08-12 |
RU2278515C2 (ru) | 2006-06-27 |
CZ2003509A3 (cs) | 2003-06-18 |
NO328900B1 (no) | 2010-06-07 |
NO20030730D0 (no) | 2003-02-14 |
EP1671542A1 (de) | 2006-06-21 |
US20030199490A1 (en) | 2003-10-23 |
PL366200A1 (en) | 2005-01-24 |
EP1313368A1 (de) | 2003-05-28 |
CN1287667C (zh) | 2006-12-06 |
NO20030730L (no) | 2003-03-28 |
WO2002015693A9 (de) | 2002-06-06 |
AU2001291778A1 (en) | 2002-03-04 |
EP2033519A1 (de) | 2009-03-11 |
ES2314769T3 (es) | 2009-03-16 |
PT1671542E (pt) | 2008-12-17 |
DE50114436D1 (de) | 2008-11-27 |
BRPI0113384B1 (pt) | 2015-09-01 |
EP1671542B1 (de) | 2008-10-15 |
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