CN1135066C - 微乳液昆虫控制组合物 - Google Patents
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Abstract
本文公开了含有杀菌剂或其它昆虫控制试剂的微乳液。微乳液具有高含量的烃,而使用相对低量的乳化剂。微乳液也可以以气雾剂或液体形式释放卫生消毒剂。
Description
本发明涉及含有昆虫控制试剂和也有卫生消毒剂的水性微乳液。这些微乳液含有较高含量的烃类溶剂和相对低含量的乳化剂。
烃类溶剂有助于消灭昆虫是为人所知。但是,烃价格昂贵,不利于环境以及易燃。所以有一种趋势就是通过水性乳液释放控制昆虫的试剂。例如参见美国专利5,145,604。本专利和在这儿所指的所有其它出版物的公开内容被引入作为参考文献,如同已完全列于此处。
US-A-4 536 323公开了用于气雾剂散布器的挥发剂组合物,包括水包油型微乳液,微乳液含有用于挥发剂的与水不混溶的溶剂,水和混合表面活性剂体系。组合物的最终用途公开于US-A-4 536 323的第7列,33-53行。
HU-A-62 649的Derwent文摘公开了用于气雾剂产品的水包油型微乳液,包括水,溶剂,磺酸酯表面活性剂,30-47%重量的脂族碳水化合物,1-5%重量“添加剂”和0~3%重量活性杀虫试剂。
优选油相连续(油包水)乳液,因为它们被认为可以更快地消灭昆虫(是因为更好的穿透昆虫的疏水性表皮)。同样它们优选也因为它们一般不会产生过量的泡沫。
但是,这些油相连续型标准型(宏观型)乳液本身不易稳定,在长期贮存(如在气雾剂容器中)过程中形成分离相。因此要求使用者在就要喷洒产品之前用力摇晃。需要摇晃是一种限制,使得这种类型的产品除了以气雾剂形式之外很少在商业上碰到。
而且,所知的标准型乳液,特别是油相连续型,并不能产生较好的杀菌剂活性。确实,烃类溶剂的存在似乎影响了抗微生物活性,大概是因为隔开了有效地进入油相中的杀菌剂,在油相中得不到杀菌剂去攻击微生物的细胞壁。同样,经常是这种标准型乳液组分的非离子乳化剂有时可能影响杀菌剂活性。
因此本领域研制了更加稳定的微乳液,它含有水,烃,杀虫剂以及一种或多种乳化剂。例如参见美国专利5,037,653。在此应用方面,“微乳液”是油和水的透明和稳定的分散体,其中分散相包括大部分具有直径为10~100毫微米的小液滴。
微乳液可能是水相连续,油相连续或两相连续。基于使用宏观乳液的经验,希望油相连续微乳液可能是消灭昆虫的最佳类型。但是,这对微乳液证明是不正确的,其中油/水微乳液不同类型的灭虫性能是相同的。
在任何一种情况中,现有技术的微乳液基杀虫剂一般含相当低的烃量(由此灭虫性能比最佳的要差),或者使用大量的乳化剂去乳化高含量的烃。对于释放昆虫控制试剂,使用大量乳化剂是不可取的。除了这种乳化剂经常是相当贵的事实之外,它们可能在喷洒杀虫剂的表面上留下不想要的残余物,如果以气雾剂形式喷洒到空气中它们可能会使人发炎。
进一步复杂化的情况是当以气雾剂形式提供微乳液时希望有一致的,平稳的以及无泡沫的喷洒图形。例如,如果在使用之前摇晃并没有完成,需要摇晃的体系可能导致较差的喷洒图形。而且泡沫可以大大地打乱了喷洒图形。
因此,存在改进的基于微乳液的控制昆虫组合物的需要,特别是那些适合于以气雾剂形式释放的组合物。
一方面,本发明提供一种微乳液(优选水包油微乳液)。在微乳液中总的烃类溶剂大于20%而低于60%(重量)。在使用烃挥发剂的地方它形成了烃类溶剂的一部分,除了挥发剂,烃溶剂部分优选是总微乳液的15%~35%(重量)。
表面活性剂是微乳液的2%~7.5%(重量),优选低于6%。至少微乳液的10%(重量)是水,优选大于30%,同样有控制昆虫试剂如杀虫活性的毒剂。
上述的微乳液特别适合于以气雾剂形式释放。因此,优选微乳液的5%(重量)或更多(如10~20%)是分散在微乳液油相中的烃挥发剂。
大量不同的气态碳烃可以用于这一用途。一般它们在气雾剂容器的压力条件下液化并成为烃溶剂的一部分。例如挥发剂可以是二甲醚,二氟乙烷,丙烷,丁烷,异丁烷以及它们的混合物。一种特别优选的挥发剂是Phillips Petroleum公司的A-70,它是丙烷/异丁烷45/55(摩尔%)的混合物。另一种是Phillips Petroleum公司的B-70,它是丙烷/正丁烷/异丁烷55/27/18(摩尔%)的混合物。在这方面应用中,“烃”中仅有碳和氢。
表面活性剂可以是阳离子,阴离子,两性和非离子表面活性剂。但是优选使用阴离子表面活性剂和非离子表面活性剂的混合物,参见EP677,579。
特别优选的是异丙胺磺酸盐(Calimulse PRS;Pilot chemical)和三苯乙烯基苯酚,如三苯乙烯基苯酚乙氧基化物(Soprophor BSU;RhonePoulenc),基本上等量的混合物。其它适合的非离子表面活性剂是Soprophors 4D 384和FL,和衍生于在醇烷基链上有8~24个碳原子的伯和伯脂肪醇的聚乙氧基化物。另外,部分或全部环氧乙烷可被环氧丙烷取代。
其它适合的非离子表面活性剂是聚亚氧烷基烷基苯酚;酸疏水链有8或更多个碳原子的高级有机酸和10或更多摩尔环氧乙烷作为亲水基团的聚亚烷基酯;聚亚烷基烷基胺,它的疏水基团是来自伯,仲或叔胺以及它的环氧乙烷含量足够高以赋于水溶性和非离子特性,通常衍生于具有8个或更多碳原子的脂肪酸;聚亚烷基烷基酰胺,它具有衍生于脂肪酸或酯的酰胺的疏水基团;甘醇的脂肪酸酯,聚亚烷基环氧嵌段共聚物。
适合的阴离子表面活性剂是烷基基团中有6~20个碳原子的烷基芳基磺酸盐;C10~C22脂肪酸皂;C10~C22脂肪硫酸盐;C10~C22烷基磺酸盐,包括高级烷基和线性链烷烃磺酸的碱金属盐和它们的盐;二烷基磺基琥珀酸碱金属盐,乙氧基化醇硫酸盐,磷酸酯,牛磺酸盐等。其它表面活性剂参见美国专利5,037,653。
本发明微乳液的一个重要优点是它们可以释放卫生消毒剂而没有严重影响它的抗菌活性。如这儿使用的,“卫生消毒剂”可减少细菌的数量。它也可杀死病毒,真菌以及藻类。优选的卫生消毒剂是杀菌酚类。特别优选的杀菌酚是Dow Chemical公司出售的,商品名为Dowicide。Dowicide 1就是一种,它是邻苯基苯酚。其它烷基,芳基,和/或卤素取代的酚类也是优选的杀菌剂(如4-氯-3,5-二甲基苯酚,4-特戊基苯酚)。另一种卫生消毒剂是Nipa Labs的Nipacide BCP,它是苄基氯苯酚。其它适合的卫生消毒剂是邻氯苯酚,2-溴-2-硝基丙烷-1,3-二醇,各种各样的季铵盐,三丁基锡衍生物等等。
有效杀虫毒剂是最优选的控制昆虫试剂,特别是那些对爬行型类昆虫有效的试剂。它们也可以是对飞虫类有效的试剂。实例有合成的拟除虫菊酯(如氯氰菊酯,氟氯氰菊酯和氯氟氰菊酯),天然的除虫菊(如除虫菊酯),以及有机磷酸酯例如毒死蜱。其它合成拟除虫菊酯的实例有烯丙菊酯forte,苯醚菊酯,d-苯醚菊酯,胺菊酯,苄呋菊酯,S-生物烯丙菊酯,丙烯除虫菊酯,氯菊酯,d-反式丙烯除虫菊酯和噻嗯菊酯。也可参见美国专利5,037,653中所列的杀虫剂。
另外,控制昆虫试剂可以是驱虫剂如茅香油,柠檬草油,熏衣草油,肉桂油,印度栋树油,丁子草油,檀香油或香叶醇。如果需要,试剂也可以是昆虫生长控制剂如烯虫乙酯。
大量不同的烃溶剂可以被使用(除了挥发剂)。优选,这些非挥发剂的烃有6~20个碳原子。实例有己烷,苯,甲苯,二甲苯,矿物精;矿物油,1,8-萜二烯,重芳香族石脑油,煤油,石蜡,以及其它烷烃和烯烃。特别优选的烃是牌号为Exxsol的烃,它来自Exxon/Esso公司。这些一般是低于C20烃的混合物(烷烃,烯烃)。特别优选的是Exxsol D-95和Exxsol D-60。后者是萘和环烷的混合物。
为了在极低含量乳化剂下得到可接受的性能,也优选使用助溶剂醇。优选添加有机伯醇的混合物。一种溶剂可以是具有3~12个碳原子的脂肪族伯醇(例如,1-辛醇,1-己醇,1-戊醇,或1-丁醇)。另一种助溶剂可以是少于20个碳原子的非芳族醚醇(例如,二甘醇单己基醚,二甘醇单丁基醚,或丙二醇单丁基醚)。同样也可以加入某些二醇如己二醇,三甘醇,或1,4-丁二醇。
当微乳液含有气态挥发剂并且被加压时,微乳液就可以从气雾剂容器中喷洒出来。另外,一种泵喷射容器(没有挥发剂)也可以被使用。喷剂可以喷入空气中,表面上或直接对着昆虫。因为喷剂是微乳液,所以它是十分稳定的。因此,如果气雾剂容器在生产厂中已被摇晃,则消费者不需要在使用之前摇晃。
另外,因为烃的含量较高,所以微乳液有极出色的灭虫性能。而且在水包油的微乳液形式中(尽管烃的含量高)易燃性是较低,可以接受。因为乳化剂表面活性剂的含量是很低,几乎没有可见的残留物或由于表面活性剂使人发炎的雾化颗粒。而且基本上没有泡沫,并且喷剂喷射出奇地一致和平稳。
本发明的微乳液也允许释放可以提供极好抗微生物活性的卫生消毒剂。
一个使用本发明的优选方式就是喷洒昆虫将爬过的表面,然后让昆虫爬过该表面。用这种方法可以被杀死的昆虫有蟑螂,蚂蚁,蟋蟀,地蜈蚣,蠹鱼以及其它经常在建筑物中会找到的爬虫。另外,可以使用微乳液通过喷洒空气杀死各种不同的飞虫如蚊子,苍蝇,黄蜂,大黄蜂等。
也可以加入增效剂以增加杀虫剂的有效性。实例有胡椒基丁醚(Butacide;AgrEvo)。
优选在上述的微乳液中使用去离子水。但是一般的自来水可以用。同样也可以加入其它标准添加剂如腐蚀抑制剂和芳香剂。
微乳液的优选pH范围是pH6~pH8。pH值太低可以导致容器腐蚀并且也可能影响被喷洒的表面。pH值太高可以对活性组分产生不利影响,并且也可能对喷洒的表面产生不利影响。
本发明的目的包括提供一种具有控制昆虫试剂的微乳液:
(a)它不要求消费者在使用之前摇晃;
(b)它具有好的灭虫性能;
(c)它的生产相当便宜;
(d)使用时它不留下难以接受的表面活性剂残余物;
(e)它适合于以气雾剂形式释放并且提供一平稳,一致和无泡沫的喷洒图形;
(f)它可以释放有效的卫生消毒剂而没有明显地降低它的活性。
本发明的这些和其它目的和优点(如使用这种微乳液的方法)在下面的描述中会很明显。下面的描述只是优选实施方案。因此,为了理解本发明的整个范围需要看权利要求。
实施本发明的最佳方法
实验
成份 | 作用 | 优选范围 | 实例 |
除虫菊(20%活性) | 杀虫剂 | 1-1.25% | 1% |
胡椒基丁醚 | 增效剂 | 0.5-0.63% | 0.5% |
氯菊酯92% | 杀虫剂 | 0.15-0.25% | 0.22% |
邻苯基苯酚 | 卫生消毒剂 | 0-0.44% | 0.1% |
EXXSOL D-95 | 烃溶剂 | 15-35% | 25% |
异丙胺磺酸盐 | 阴离子表面活性剂乳化剂 | 1.5-5% | 2% |
聚氧乙烯聚芳基苯基醚(Sopropheor BSU) | 非离子表面活性剂-乳化剂 | 1.5-2.5% | 2% |
1-辛醇 | 助溶剂 | 1.2-1.5% | 1.4% |
二甘醇单己基醚 | 助溶剂 | 4-11% | 8% |
芳香剂 | 芳香剂 | <0.3% | 0.2% |
Elfugin AKT 300%液体* | 腐蚀抑制剂 | 0-0.3% | 0.25% |
自来水 | 35-50% | 41.33% | |
A-70丙烷-异丁烷混合物 | 烃挥发剂 | 0-20% | 18% |
*这是Clariant公司生产的磷酸酯混合物。
对爬虫的试验
作为测试本发明微乳液的有效性我们进行了各种这种乳液的直接喷洒灭虫测试。在一组实验中,测试的准备工作包括用CO2将七星期犬的成年雄性德国蟑螂麻醉,然后分类,将它们放进干净的涂有润滑油的Tri-State 15-A塑料杯中。允许蟑螂从CO2中恢复,在测试之前没有食物和水最少1个小时。
在马上进行测试之前,将虫转移到干净的涂有润滑油的丙烯酸树脂环中(5cm高×10cm直径),环的底部结合有铝网(6×7目/cm)。在准备工作和恢复之后,蟑螂测试容器(一次一个)被放入一喷洒塔中并进行靶向喷洒(18秒钟0.5克)。喷洒塔是一个机械结构,它从一测定的和一致的距离向目标释放均匀量的喷剂,以此便于可靠地比较喷洒材料的影响。在每次喷洒之后,蟑螂马上转移到一干净的涂有润滑油的玻璃电瓶壳中进行选定时期的观察。一般,99%或更多的虫在两分钟内死去。
对美国蟑螂进行了优选配方的同样测试。又一次,配方十分有效地快速杀死99%或更多虫(接触后少于五分钟内)。
我们使用EPA测试协议(DIS/TSS-10,1992年1月7日)测试了我们优选组合物的卫生消毒能力以证明一种产品是“卫生消毒剂”。基本上,多个该组合物的制备品,其中至少一个有60天之久,在胶木砖和陶瓷砖上进行对Staphlococcus aureus和klebsiellapneumoniae的数量进行测试。进行平行的对照测试,在不超过五分钟的接触之后,细菌比平行对照数量下降至少99.9%。
应当注意的是上面的描述仅仅涉及本发明的几个优选形式。其它形式也是可能的。例如,可以通过增加挥发剂含量至具体范围的上限部分制成杀飞虫剂。同样也可使用大量不同的其它控制昆虫试剂,卫生消毒剂和乳化剂。
本发明提供了在建筑物和其它环境中使用的杀虫剂和其它控制昆虫试剂。
Claims (13)
1.一种微乳液,其pH值为6-8和具有一半以上的小液滴是直径为10~100毫微米的小液滴,特征在于包括:
a.烃类溶剂,它是大于微乳液的20%重量,低于60%重量;
b.表面活性剂,它是大于微乳液的2%重量,低于7.5%重量;
c.卫生消毒剂,是一种杀菌苯酚类;
d.至少10%重量的水;
e.一种控制昆虫试剂,选自合成拟除虫菊酯、天然除虫菊、毒死蜱、茅香油、柠檬草油、熏衣草油、肉桂油、印度楝树油、丁子草油、檀香油、香叶醇和烯虫乙酯。
2.权利要求1的微乳液,其中微乳液是水包油的微乳液。
3.权利要求2的微乳液,其中有少于6%重量的表面活性剂。
4.权利要求2的微乳液,其中至少10%重量的微乳液是烃抛射剂以及少于35%重量的微乳液是除了抛射剂的烃溶剂。
5.权利要求4的微乳液,其中抛射剂是选自二甲醚,二氟乙烷,丙烷,丁烷,以及它们的混合物。
6.权利要求2的微乳液,其中表面活性剂包括阴离子表面活性剂和非离子表面活性剂。
7.权利要求1的微乳液,其中苯酚类是邻苯基苯酚。
8.权利要求2的微乳液,它另外包括一种是有机醇的助溶剂。
9.权利要求8的微乳液,其中有机醇包括:
有3~12个碳原子的伯醇;以及
有少于20个碳原子的醚醇。
10.权利要求9的微乳液,其中伯醇是1-辛醇和醚醇是二甘醇单己基醚。
11.权利要求4的微乳液,其中微乳液是在一种气雾喷剂中。
12.杀死爬虫的方法,它包括:
将权利要求2的微乳液施用在一表面;
允许虫从该表面爬过。
13.权利要求12的方法,其中昆虫有蟑螂,蚂蚁,蟋蟀,地娱蚣以及蠹鱼。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/671,742 US5792465A (en) | 1996-06-28 | 1996-06-28 | Microemulsion insect control compositions containing phenol |
US08/671,742 | 1996-06-28 |
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CN1226133A CN1226133A (zh) | 1999-08-18 |
CN1135066C true CN1135066C (zh) | 2004-01-21 |
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CNB971967911A Expired - Fee Related CN1135066C (zh) | 1996-06-28 | 1997-06-26 | 微乳液昆虫控制组合物 |
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US (1) | US5792465A (zh) |
EP (1) | EP0907317B1 (zh) |
JP (1) | JP2000513376A (zh) |
KR (1) | KR20000022288A (zh) |
CN (1) | CN1135066C (zh) |
AR (1) | AR007651A1 (zh) |
AT (1) | ATE231334T1 (zh) |
AU (1) | AU3505597A (zh) |
BR (1) | BR9710076A (zh) |
CA (1) | CA2259294C (zh) |
CZ (1) | CZ430298A3 (zh) |
DE (1) | DE69718640T2 (zh) |
EG (1) | EG20869A (zh) |
ES (1) | ES2185953T3 (zh) |
HU (1) | HUP9903830A3 (zh) |
ID (1) | ID17538A (zh) |
NZ (1) | NZ333626A (zh) |
PL (1) | PL330901A1 (zh) |
RU (1) | RU2191508C2 (zh) |
TR (1) | TR199802724T2 (zh) |
TW (1) | TW406007B (zh) |
UA (1) | UA41480C2 (zh) |
WO (1) | WO1998000010A1 (zh) |
ZA (1) | ZA975686B (zh) |
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- 1997-06-26 EP EP97931424A patent/EP0907317B1/en not_active Expired - Lifetime
- 1997-06-26 RU RU99101794/13A patent/RU2191508C2/ru not_active IP Right Cessation
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- 1997-06-26 AU AU35055/97A patent/AU3505597A/en not_active Abandoned
- 1997-06-26 BR BR9710076A patent/BR9710076A/pt not_active Application Discontinuation
- 1997-06-26 TR TR1998/02724T patent/TR199802724T2/xx unknown
- 1997-06-26 DE DE69718640T patent/DE69718640T2/de not_active Expired - Fee Related
- 1997-06-26 UA UA98126940A patent/UA41480C2/uk unknown
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- 1997-06-26 CA CA002259294A patent/CA2259294C/en not_active Expired - Fee Related
- 1997-06-26 WO PCT/US1997/011103 patent/WO1998000010A1/en not_active Application Discontinuation
- 1997-06-26 CN CNB971967911A patent/CN1135066C/zh not_active Expired - Fee Related
- 1997-06-26 ZA ZA9705686A patent/ZA975686B/xx unknown
- 1997-06-26 CZ CZ984302A patent/CZ430298A3/cs unknown
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- 1997-06-27 AR ARP970102861A patent/AR007651A1/es active IP Right Grant
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Cited By (1)
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CN103689016A (zh) * | 2013-12-30 | 2014-04-02 | 青岛崂乡茶制品有限公司 | 一种用于茶叶种植的杀虫剂 |
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CN1226133A (zh) | 1999-08-18 |
ID17538A (id) | 1998-01-08 |
UA41480C2 (uk) | 2001-09-17 |
WO1998000010A1 (en) | 1998-01-08 |
DE69718640T2 (de) | 2003-10-23 |
US5792465A (en) | 1998-08-11 |
AR007651A1 (es) | 1999-11-10 |
EG20869A (en) | 2000-05-31 |
EP0907317A1 (en) | 1999-04-14 |
PL330901A1 (en) | 1999-06-07 |
DE69718640D1 (de) | 2003-02-27 |
ZA975686B (en) | 1998-01-23 |
TR199802724T2 (xx) | 1999-03-22 |
HUP9903830A2 (hu) | 2000-03-28 |
CA2259294A1 (en) | 1998-01-08 |
RU2191508C2 (ru) | 2002-10-27 |
JP2000513376A (ja) | 2000-10-10 |
CZ430298A3 (cs) | 1999-07-14 |
NZ333626A (en) | 2000-02-28 |
AU3505597A (en) | 1998-01-21 |
TW406007B (en) | 2000-09-21 |
ES2185953T3 (es) | 2003-05-01 |
BR9710076A (pt) | 1999-08-10 |
EP0907317B1 (en) | 2003-01-22 |
KR20000022288A (ko) | 2000-04-25 |
ATE231334T1 (de) | 2003-02-15 |
HUP9903830A3 (en) | 2002-03-28 |
CA2259294C (en) | 2002-06-18 |
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