CN103461361B - 唑嘧磺草胺或双氯磺草胺与吡啶硫酮锌的协同组合 - Google Patents

唑嘧磺草胺或双氯磺草胺与吡啶硫酮锌的协同组合 Download PDF

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CN103461361B
CN103461361B CN201310455213.9A CN201310455213A CN103461361B CN 103461361 B CN103461361 B CN 103461361B CN 201310455213 A CN201310455213 A CN 201310455213A CN 103461361 B CN103461361 B CN 103461361B
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E·西亚纳瓦特
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    • AHUMAN NECESSITIES
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    • A01N2300/00Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48

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Abstract

本发明揭示一种含唑嘧磺草胺或双氯磺草胺和吡啶硫酮锌的协同抗微生物组合物。

Description

唑嘧磺草胺或双氯磺草胺与吡啶硫酮锌的协同组合
本申请是申请日为2011年11月3日,进入中国国家阶段的申请号为201110364547.6,名称为“唑嘧磺草胺或双氯磺草胺与吡啶硫酮锌的协同组合”的发明专利申请的分案申请。
技术领域
本发明涉及杀生物剂的组合,该组合具有比单独的抗微生物化合物更高的活性。
背景技术
使用至少两种抗微生物化合物的组合能拓宽潜在的市场,减少使用浓度和成本,并减少废物。在一些情况下,由于市售的抗微生物化合物对某些种类的微生物(例如对一些抗微生物化合物具有耐受性的微生物)的活性很差,即使采用高使用浓度,所述市售的抗微生物化合物也无法提供有效的微生物控制。有时人们使用不同抗微生物化合物的组合在具体最终应用环境中提供微生物的总体控制。例如,美国专利第5,591,760号揭示了3-碘-2-丙炔基-丁基氨基甲酸酯(IPBC)和4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(DCOIT)的组合,但是该参考文献没有暗示本发明要求保护的任何组合。而且,目前需要其它的抗微生物化合物的组合,该组合对各种不同的微生物菌株具有增强的活性,从而能有效控制微生物,尤其是在干膜涂层中。本发明所解决的问题是提供这些其它的抗微生物化合物的组合。
发明内容
本发明涉及一种协同抗微生物组合物,其包含:(a)唑嘧磺草胺或双氯磺草胺;和(b)吡啶硫酮锌(ZPT);其中唑嘧磺草胺与吡啶硫酮锌的重量比为8:1-1:7,双氯磺草胺与吡啶硫酮锌的重量比为15:1-1:2。
具体实施方式
在本文中,除非上下文明确有不同的说明,以下术语具有所限定的含义。唑嘧磺草胺是N-(2,6-二氟苯基)-5-甲基[1,2,4]三唑并[1,5-a]嘧啶-2-磺酰胺。双氯磺草胺是N-(2,6-二氯苯基)-5-乙氧基-7-氟[1,2,4]三唑并[1,5-c]嘧啶-2-磺酰胺。术语"抗微生物化合物"表示能够抑制或控制微生物生长的化合物;抗微生物化合物包括杀细菌剂、细菌抑制剂(bacteristats)、杀真菌剂、真菌抑制剂、杀藻剂和藻抑制剂,具体取决于所用的剂量,体系条件,以及所需的微生物控制水平。术语“微生物”包括例如真菌(例如酵母菌和霉菌)、细菌和藻类。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 Culture Collection),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(重量%)。本发明组合物中抗微生物化合物的百分含量是基于组合物中活性成分的总重量,即是基于抗微生物化合物本身,而不包括任何可能存在的溶剂、载体、分散剂、稳定剂或其它材料的量。
较佳地,当抗微生物组合物包含唑嘧磺草胺和ZPT时,唑嘧磺草胺与ZPT的重量比为8:1-1:6,优选为7:1-1:7,优选为8:1-1:5;优选为7:1-1:6;优选为7:1-1:5;优选为6:1-1:6;优选为6:1-1:5。
较佳地,当抗微生物组合物包含双氯磺草胺和ZPT时,双氯磺草胺与ZPT的重量比为12:1-1:2,优选为10:1-1:2,优选为10:1-1:1.5;优选为10:1-1:1。
较佳地,使用双氯磺草胺与ZPT的组合来抑制藻类在水性介质中的生长。较佳地,双氯磺草胺与ZPT的比例为15:1-1:2,优选为12:1-1:2,优选为10:1-1:2;优选为10:1-1:1.5;优选为10:1-1:1。
上述抗微生物组合物可包含唑嘧磺草胺和双氯磺草胺中的任一种或两种和/或其它杀生物剂。通常,抗微生物组合物用于抑制藻类和/或真菌的生长。
较佳地,将本发明的抗微生物组合引入液体组合物中,特别是引入在水性介质中的聚合物分散体中。杀生物剂组合特别适用于以下材料的防护:建筑材料如粘合剂,填缝剂,填缝混合料,密封剂,壁板等,漆,涂料,聚合物,塑料,合成橡胶和天然橡胶,纸产品,玻璃纤维片,绝缘/绝热材料,外部绝缘/绝热精饰系统,屋顶油毡和铺地毡,建筑石膏,木产品和木-塑料复合物。较佳地,抗微生物组合物是含文中所述的杀生物剂组合的乳胶漆或其它液体涂料组合物。杀生物剂组合物可用于施涂漆或其它液体涂料组合物后得到的干膜涂层的防护。较佳地,抗微生物组合物是包含一种或多种文中所述的杀生物剂组合的丙烯酸类乳胶漆,或将该漆施涂到表面后得到的干膜涂层。
通常,为控制微生物生长,本发明杀生物剂组合的量应为100ppm-10,000ppm活性成分。较佳的,组合物中活性成分的含量至少为300ppm,优选至少为500ppm,优选至少为600ppm,优选至少为700ppm。较佳地,组合物中活性成分的含量不超过8,000ppm,优选不超过6,000ppm,优选不超过5,000ppm,优选不超过4,000ppm,优选不超过3,000ppm,优选不超过2500ppm,优选不超过2,000ppm,优选不超过1,800ppm,优选不超过1,600ppm。上述浓度是指含杀生物剂组合的液体组合物中的浓度;干膜涂层中的杀生物剂含量更高。
本发明还包括防止建筑材料中(特别是干膜涂层中)微生物生长的方法,该方法是将所述的任何杀生物剂组合引入所述材料中。
实施例
样品制备:将单独一种杀生物剂或杀生物剂的混合物后加入不含杀生物剂的白色丙烯酸类乳胶漆中,得到最高总活性成分测试浓度。然后,用不含杀生物剂的丙烯酸类乳胶漆稀释上述漆,得到用于测试的目标浓度。根据所测试的杀生物剂混合物的类型,杀生物剂总浓度在200-5000ppm的范围内。在杀生物剂加入或稀释后,将各样品手动混合至少1分钟,直到均匀。利用3密耳(0.0762毫米)伯德(Bird)棒施涂器,使用各漆样品和对照样品(不含杀生物剂)在黑色塑料-氯乙烯/乙酸乙烯酯共聚物板(勒内塔有限公司(LENETA,Mahwah,NJ))上制备膜。将这些板在避免直接暴露于日光的情况下彻底干燥至少2天。从各板上切下正方形盘(0.5英寸2;1.27厘米2),用作杀真菌和杀藻类效力测试的基板。当样品盘被置于测试板的孔中时,上述样品尺寸与琼脂边界吻合。各样品的测试重复进行两次。
测试条件:使用合适的培养基(对于绿藻纲植物(Chlorophytes)使用BOLD’S3N,对于蓝藻(Cyanobacteria)使用BG-11,对于真菌使用PDA)支持微生物生长。对于藻类,将测试板在室温(25℃-26℃),在周期性的亮-暗环境中保持四周。将用于抗真菌测试的板在30℃保持四周。在培育结束时,评分样品中可见微生物生长所覆盖的面积百分数。
藻类接种物
真菌接种物
抗藻类效力测试–改进的ASTM5589
ASTM5589是确定各种涂料(包括漆)对藻类损害的耐受性的标准快速测试方法。为作高通量筛选,该方法的规模从培养皿缩小到6孔板。用一对无菌镊子将单个试样放置在琼脂塞中央(在琼脂塞上),上过漆的表面向上。将等浓度(1X106cfu/ml)和等体积(取决于要接种的样品数)的类似生长的生物体混合,由此制得藻类接种物。
在唑嘧磺草胺+各种IT协同研究中,制备混合藻的三种合并物(pool)作为测试接种物:BG-11培养基上生长的粘球藻属和颤藻属,一种蓝藻混合物;小球藻(Chlorella sp.)、绿球藻(Chlorella kessleri)和地木耳(Nostoccommune)是混合并在Bold培养基上生长的单细胞绿藻;橘色藻变种(Trentepohlia aurea)、芬芳橘色藻(Tretepohlia odorata)和墙壁眉藻(Calotrixparientina)是混合并在Bold培养基上生长的丝状藻类。
在双氯磺草胺+各种IT协同研究中,仅制备混合藻类的两种合并物:BG-11培养基上生长的粘球藻属和颤藻属,在Bold培养基上生长的小球藻(Chlorella sp.)、绿球藻(Chlorella kessleri)、地木耳(Nostoc commune)、橘色藻变种(Trentepohlia aurea)、芬芳橘色藻(Tretepohlia odorata)和墙壁眉藻(Calotrix parientina)。
用400μl生物体混合物(1X106cfu/ml)接种含测试试样的各孔,确保整个表面(漆膜以及周围的琼脂)被均匀覆盖。在室温下(25℃-26℃),通过周期性地暴露于亮(OTT-Lite型号OTL4012P,40瓦,26千流明)-暗环境四周来培育上述板。在各周结束时,根据被覆盖的面积百分数以5%的幅度增加来评价总覆盖面积。
抗真菌效力测试–改进的ASTM5590
ASTM5590是确定各种涂料(包括漆)对真菌损害的耐受性的标准快速测试方法。为作高通量筛选,该方法的规模从培养皿缩小到6孔板。为了进行测试,将琼脂塞放在无菌6孔板各孔的底部。用一对无菌镊子将单个试样放置在琼脂塞中央(在琼脂塞上),上过漆的表面向上。将等浓度(1X106cfu/ml)和等体积(取决于待测试的样品数)的类似生长的生物体混合,由此制得真菌接种物。对于唑嘧磺草胺+各种IT协同研究,制备混合真菌的三种合并物作为测试接种物。多主枝孢与出芽短梗孢混合;黑曲霉与绳状青霉(Penicillium funiculosum)混合,链格孢与绿色木霉混合。对于双氯磺草胺+各种IT协同研究,所有上述真菌混合作为单个合并物。用400μl生物体混合物(1X106cfu/ml)接种各孔,确保整个表面(漆膜以及周围的琼脂)被均匀覆盖。在潮湿环境下,将上述板在30℃培育四周。在第二周后,在各周结束时评价和记录所覆盖的总面积百分数,记录为5%的增量。
协同指数计算
协同指数(SI)
根据F.C.Kull等的Al.方法(应用微生物学(Applied Microbiology),第9卷(1961))计算SI。在该研究中,根据以下公式计算SI,最小抑制浓度是基于各杀生物剂对各测试微生物的抑制百分数所选择的。
SI=Qa/QA+Qb/QB
Qa=混合物中杀生物剂A的浓度
QA=杀生物剂A作为唯一的杀生物剂的浓度
Qb=混合物中杀生物剂B的浓度
QB=杀生物剂B作为唯一的杀生物剂的浓度
在公式中,如果SI值<1,则表明混合杀生物剂存在协同效应。
注:如果最高测试浓度的活性成分没有表现出一定的抑制作用,则该最高浓度是用来计算预估的SI,引入“<”记号表示需要更高的活性成分浓度来实现目标抑制
NE=在测试浓度中无端点符合各SI计算中设定的百分抑制标准
唑嘧磺草胺和ZPT的协同研究
双氯磺草胺和ZPT的协同研究

Claims (4)

1.一种协同抗微生物组合物,其包含双氯磺草胺和吡啶硫酮锌;其中双氯磺草胺与吡啶硫酮锌的重量比为10:1-1:2。
2.如权利要求1所述的组合物,其特征在于,该组合物是建筑材料。
3.如权利要求2所述的组合物,其特征在于,所述建筑材料是漆、聚合物。
4.如权利要求2所述的组合物,其特征在于,所述建筑材料是涂料、塑料、合成橡胶或天然橡胶、纸产品、玻璃纤维片、绝缘/绝热材料、外部绝缘/绝热精饰系统、屋顶油毡或铺地毡、建筑石膏、木产品或木-塑料复合物。
CN201310455213.9A 2010-11-09 2011-11-03 唑嘧磺草胺或双氯磺草胺与吡啶硫酮锌的协同组合 Expired - Fee Related CN103461361B (zh)

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CN103461361A (zh) 2013-12-25
RU2566715C2 (ru) 2015-10-27
EP2481285A2 (en) 2012-08-01
EP2481285A3 (en) 2012-12-26
CN102461525A (zh) 2012-05-23
BRPI1105285A2 (pt) 2013-03-05
BRPI1105285B1 (pt) 2018-01-02
KR20120049830A (ko) 2012-05-17
US20120115834A1 (en) 2012-05-10
JP5364935B2 (ja) 2013-12-11
US8501725B2 (en) 2013-08-06
JP2012102081A (ja) 2012-05-31
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RU2011144304A (ru) 2013-05-10

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