CN1043292C - 含有丁基氨基甲酸碘炔丙酯和2-巯基n-氧化吡啶的钠盐的抗微生物组合物及其应用 - Google Patents

含有丁基氨基甲酸碘炔丙酯和2-巯基n-氧化吡啶的钠盐的抗微生物组合物及其应用 Download PDF

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CN1043292C
CN1043292C CN91111932A CN91111932A CN1043292C CN 1043292 C CN1043292 C CN 1043292C CN 91111932 A CN91111932 A CN 91111932A CN 91111932 A CN91111932 A CN 91111932A CN 1043292 C CN1043292 C CN 1043292C
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R·J·梅塔
S·E·舍伯
B·C·兰格
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    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract

一种协同抗微生物组合物,含有具有协同作用的和具有一定比率的2-疏基-N-氧化吡啶及其盐和丁基氨基甲酸磺炔丙酯。

Description

含有丁基氨基甲酸碘炔丙酯和2-巯基N-氧化吡啶的钠盐的抗微生物组合物及其应用
本发明涉及抗微生物组合物及控制微生物的方法。
微生物存在于各种含水体系中,例如乳液、油漆、涂料、冷却水体系和人工池塘等。它们能引起这些体系的变质与损坏。例如,上了漆的表面因看不见的微生物的集结而损毁了外形,因此破坏了油漆制品的整体美感;冷却塔因微生物在表面集结而失去效力,因此降低了塔的热传递能力。常规的方法是通过引入各种具有抗微生物活性的添加剂或它们的组合实现抑制这些体系微生物的变质。
已经有多种物质用于控制不同环境中的微生物,其中一些是:氯/溴化合物、戊二醛、异噻唑啉酮、有机锡制剂、铜盐、季铵化合物(SD Strauss and PR Puckorius inJ、Power,SI,1984年6月)和三嗪。每种物质都缺乏对毒性、pH和温度的敏感性、限制性作用、化学稳定性和/或相容性。
由于上述常规抗微生物化合物的效果不良,因此需要可以以低剂量率使用的更有效的抗微生物剂,它们对于最终的用途具有更有价值的效力,减少了对受影响环境体系的污染,并且减少了对附近非目标生物体如水生动物和有用的作物等的副作用。
在所推荐的很多抗微生物化合物中,只有相当少量的在实践中是有用的,其中有丁基氨基甲酸碘炔丙酯和2-巯基-N-氧化吡啶。但是就我们所知,从未有人曾建议过将这两种抗微生物剂一起使用。
本发明的目的是提供一种以很低含量的活性成分控制微生物的方法。本发明另一个目的是使用适于各种对因微生物变质敏感体系的组合物。本发明还有一个目的是提供一种在冷却塔、油漆、船用防污涂料、喷洗剂、游泳池、涂料、装饰池塘、纤维、皮革、纸、木、金属加工液、化妆制剂、燃料系统、治疗药物制剂、和类似物中控制微生物的方法,该方法没有令人讨厌的副产物气味、退色、或者其它对被处理(和控制)系统的不良作用。本发明实现了这些目的以及其它目的,并且在下文中加以说明。一方面,本发明包括一种用于控制微生物的组合物,该组合物包括(A)一种下式所示的化合物(2-巯基-N-氧化吡啶的金属盐)
Figure C9111193200051
其中M为一种选自钠、钾、钙、镁和锌的金属阳离子;当M是钠或钾时,X=1;当M是镁、钙、锌时,X=2;和(B)一种下式所示的化合物(丁基氧基甲酸碘炔丙酯)
Figure C9111193200052
其两者在一定比例下具有协同作用。另一方面,本发明包括一种抑制细菌、真菌、藻及其混合物在被它们污染的部位上生长的方法,该方法包括向该部位上(内)引入对它们生长产生不利影响的有效量的上述组合物。
本发明的另一方面是一种控制冷却塔水中微生物的方法,该方法包括保持水中上述组合物的浓度。
本发明还包括含有该抗微生物组合物的抗微生物涂料或浸渍组合物和船用防污组合物。
本发明的优选的方面是,将抗微生物组合物引入治疗药物制剂,例如,局部抗真菌治疗剂如香波、乳剂和油膏。
我们已经发现了对控制微生物特别有效的组合物,该组合物含有(A)下式化合物(2-巯基-N-氧化吡啶的金属盐)
Figure C9111193200061
其中M是选自钠、钾、钙、镁和锌的一种金属阳离子;当M是钠或钾时,X=1;当M是镁、钙或锌时,X=2;和(B)下式化合物(丁基氨基甲酸碘炔丙酯)
Figure C9111193200062
其两者比例具有协同作用。
本发明中,控制微生物的方法包括使用有效量的上述组合物。
另一个重要的应用是使涂料或浸渍组合物具有抗微生物作用,该应用包括在涂料或浸渍组合物中引入本发明的组合物,其浓度优选的约0.1ppm至约2%、更优选约1ppm至约1%、最优选约10-4000ppm。
另一方面,在船用防污组合物中,本发明的抗微生物组合物占防污组合物的约1-10%。
在治疗药物制剂如洗剂、乳剂、油膏或局部治疗剂中;在金属工作液的处理中;以及在纤维、皮革、纸或木材的保护中,所加入的抗微生物组合物的浓度是约0.1ppm至约2%重量。在含水基质中。根据具体的最终用途,抗微生物组合物占含水体系的约0.1ppm至约1%;例如,在冷却水塔使用中以及在纸浆中或造纸过程中,所加入的抗微生物组合物的浓度约为0.1-1000ppm重量。在化妆品制剂,例如润肤或润手香脂、化妆水等中;以及在燃料体系如喷气机燃料、汽油和燃料油等的处理中,所加入的抗微生物组合物的浓度约为0.1ppm至约1%重量。
抗微生物组合物也可用于建筑产品中,例如灰泥、屋顶胶粘剂、墙胶粘剂、用于水藻保护的砌筑涂料;在保护基底不受藻类浸蚀的透明涂饰剂和涂层中;用于水产养殖中的藻类控制,包括鱼缸、孵鱼卵处、虾池、鱼池、软体动物和甲壳动物养殖处;用于娱乐用或装饰性水池中的藻类控制,如游泳池、湖、喷泉、人工池;用于工业或市政用水池中的藻类控制,例如沉淀或分离池、废物处理池以及贮水池;用于溶液养殖场中的藻类控制;用于制造纸浆和纸产品过程中的藻类控制;用于塑料内含物或保护塑料抗水藻的涂层中;以及用于游泳池壁的保护塑料中或塑料的涂层中。
我们优选的组合物是其中(A)对(B)的重量比约为0.1∶100至约100∶0.1。特别优选的比率范围是约200∶1至约1∶99重量。
下面的实施例仅仅是本发明很多应用中的很少部分。这些实施例将说明本发明而不是限制本发明。在不背离本发明精神和范围的条件下,对本发明进行各种修改、改变及改进对于本领域的专家来说是显而易见的。
            实施例A.一般方法
MIC值代表最小抑制浓度。MIC定义为完全抑制特定微生物生长所需的最低含量的化合物。
协同作用定义为大于两个独立部分之和的两个变量的响应。协同作用是利用F.C.Kull,P.C.Eisman,H.D.Sylwestrowicz和R.K.Mayer所描述的计算方法(APPlied Microbiology 9,538(1961)),结合对两种化合物的研究测定的:
Figure C9111193200081
其中:
QA=化合物A单独作用、得到最小抑制浓度的量(MIC)
Qa=化合物A用于混合物中、得到最小抑制浓度的量(MIC)
QB=化合物B单独作用、得到最小抑制浓度的量(MIC)
Qb=化合物B用于混合物中、得到最小抑制浓度的量(MIC)可以得到下列SI值:
SI>1表示拮抗作用,
SI=1表示加合作用,
SI≤1表示协同作用。
用丁基氧基甲酸碘炔丙酯和2-巯基-N-氧化吡啶金属盐混合物对各种微生物进行效力研究。在胰蛋白酶大豆肉汤(TSB)培养基中,采用微滴板分析法进行MIC研究。在此方法中,通过在96孔塑料微滴板中制备2倍系列化合物的稀释液对很多浓度进行试验。所有液体基质的转移都使用校准过的单支或多支计数移液管。在合适的溶剂中制备化合物的贮备液,并将其分配在生长基质中。随后在微滴板中用所需的生长基质制备稀释液;每孔中液体的总体积为100μl。每个板含有一定浓度的两种化合物,是通过在微滴板中分两个方面连续滴定等体积的液体制备。每个板含有每种结合的对照行(只含一种成分),因此也测定了单一化合物的MIC值。实施例1.绿脓假单胞菌(Pseudomonas aeruginosa)
利用绿脓假单胞菌的纯培养物,对丁基氨基甲酸碘炔丙酯(化合物B,丙酮溶液)和2-巯基-N-氧化吡啶钠盐(化合物A)的各种结合进行MIC测定(TSB培养基)。化合物A/化合物B结合的MIC数据(ppm)
 Qa   Qb   Qa/Qb    SI
25(QA) 0      -        1.0
12.5   31     29/71    0.63
12.5   63     17/83    0.75
6.3    125    5/95     0.75
3.1    125    2/98     0.63
0      250(QB) -       1.0
所画出的图说明了试验记录,该记录用于建立化合物A/化合物B结合抗绿脓假单胞菌的协同作用关系:X=微生物生长,空格=无微生物生长。实施例2.黑曲霉(Aspergillus niger)
按照与实施例1相同的方法,进行丁基氨基甲酸碘炔丙酯(化合物B,丙酮贮备液)和2-巯基-N-氧化吡啶钠盐(化合物A)抗黑曲霉的另一项MIC研究。化合物A/化合物B结合的MIC数据(ppm)
Qa       Qb    Qa/Qb       SI
25(QA)    0        -         1.0
12.5      0.08    160/1      0.63
12.5      0.16    99/1       0.75
6.3       0.16    97/3       0.50
6.3       0.31    95/5       0.75
3.1       0.16    95/5       0.38
3.1       0.31    91/9       0.63
1.6       0.16    91/9       0.31
1.6       0.31    83/17      0.56
0.8       0.16    83/17      0.28
0.8       0.31    71/29      0.53
0.4       0.16    71/29      0.27
0.4       0.31    56/44      0.52
0.2       0.31    38/62      0.51
0.1       0.31    24/76      0.50
0        0.63(QB)-         1.0
所绘出的图说明了试验记录,该记录用于建立化合物A/化合物B结合抗黑曲霉的协同作用关系:X=微生物生长,空格=无微生物生长。
Figure C9111193200121

Claims (12)

1.杀微生物组合物,含有具有协同作用的混合物,其中第一种成分是2-巯基-N-氧化吡啶的钠盐,第二种成分是丁基氨基甲酸碘炔丙酯,第一种成分与第二种成分的比率范围是200/1至1/99。
2.权利要求1的组合物在微生物易于生长的部位控制其生长的应用,所说的微生物选自细菌、真菌、藻及其混合物。
3.权利要求2的应用,其中所述部位是含水基质,权利要求1的组合物的用量为0.1ppm至1%(重量)。
4.权利要求2的应用,其中所述部位是涂层或浸渍组合物,权利要求1的组合物的用量是0.1ppm至2%(重量)。
5.权利要求2的应用,其中所述部位是船用防污组合物,权利要求1的组合物的用量是1-10%(重量)。
6.权利要求2的应用,其中所述部位是纸浆或造纸过程,权利要求1的组合物的用量是0.1-1000ppm(重量)。
7.权利要求2的应用,其中所述部位是冷却塔水,权利要求1的组合物的用量是0.1-1000ppm(重量)。
8.权利要求2的应用,其中所述部位是金属人工液,权利要求1的组合物的用量是0.1ppm至2%(重量)。
9.权利要求2的应用,其中所述部位是纤维、皮革、纸或木材,权利要求1的组合物的用量是0.1ppm至2%(重量)。
10.权利要求2的应用,其中所述部位是化妆品制剂,权利要求1的组合物的用量是0.1ppm至1%(重量)。
11.权利要求2的应用,其中所述部位是燃料体系,权利要求1的组合物的用量是0.1-1%(重量)。
12.权利要求2的应用,其中所述部位是局部治疗药物制剂,权利要求1的组合物的用量是0.1ppm至2%(重量)。
CN91111932A 1990-11-27 1991-11-21 含有丁基氨基甲酸碘炔丙酯和2-巯基n-氧化吡啶的钠盐的抗微生物组合物及其应用 Expired - Fee Related CN1043292C (zh)

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CN1062448A (zh) 1992-07-08
AU656341B2 (en) 1995-02-02
AU8823891A (en) 1992-05-28
CA2054533A1 (en) 1992-05-28
KR920009299A (ko) 1992-06-25
JPH0558824A (ja) 1993-03-09
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JP2999875B2 (ja) 2000-01-17
CA2054533C (en) 2002-04-16

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