CN102480970B - 用于保护人类和动物的杀虫网材料 - Google Patents
用于保护人类和动物的杀虫网材料 Download PDFInfo
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- CN102480970B CN102480970B CN201080039962.8A CN201080039962A CN102480970B CN 102480970 B CN102480970 B CN 102480970B CN 201080039962 A CN201080039962 A CN 201080039962A CN 102480970 B CN102480970 B CN 102480970B
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Abstract
本发明涉及一种用包含以下组分的杀虫混合物浸渍并且适合防治建筑物中的有害昆虫且适合保护人类和动物免于该类有害昆虫及由有害昆虫传播的媒介传播性疾病的网状材料，尤其是网：a)氟唑虫清和b)一种或多种选自甲体氯氰菊酯(b1)、溴氰菊酯(b2)、氯菊酯(b3)和氯氟氰菊酯(b4)的拟除虫菊酯类，其量(各自相对于网状材料)为：a)50-150mg/m2氟唑虫清；b1)50-150mg/m2甲体氯氰菊酯；b2)15-45mg/m2溴氰菊酯；b3)50-750mg/m2氯菊酯；b4)5-30mg/m2氯氟氰菊酯。
Description
本发明涉及一种已涂布有用于保护人类和家养动物免于有害昆虫，尤其蚊虫的含拟除虫菊酯类的活性化合物混合物的片状结构，尤其是网，以及涉及一种保护人类和家养动物免于有害昆虫及由其传播的疾病的方法。
已证明对防治诸如疟疾、黄热病、登革热、淋巴丝虫病和利什曼病的媒介传播性疾病特别有效的手段是杀虫剂涂装的蚊帐。例如，除了向住宅内壁喷施杀虫剂以外，全球“RollBackMalariaPartnership”计划中的一项就是使用这类网，这是WHO(世界卫生组织)所推荐的。为了确保长时间的有效保护，必须对所述网进行涂装以使得即使在多次洗涤后仍不丧失杀虫活性。已用特定杀虫剂/粘合剂组合处理的合适的网也称为LLIN(长效杀虫网)。
目前用于这方面的杀虫剂实际上仅有拟除虫菊酯类，因为该类杀虫剂不仅兼具对昆虫的高致死效果和低哺乳动物毒性，而且也使得昆虫在能够叮咬并因此传播疾病之前因快速麻痹而无法活动(称为击昏效应)。
然而，拟除虫菊酯类已应用多年且正越来越多地应用这一事实也意味着存在抗性开始增加的风险，尤其是因为也将这些杀虫剂用于农业中以防治作物害虫。因此，例如西非和东非的冈比亚按蚊(Anophelesgambiae)以及南非的不吉按蚊(Anophelesfunestus)已产生拟除虫菊酯类抗性。
正在讨论使用替代性杀虫剂，合适的话作为与拟除虫菊酯类的混合物以破坏和避免抗性的产生。就此而言，一种可能的候选者是氟唑虫清(chlorfenapyr)，其具有良好的抗按蚊活性，对人类仅具有低度毒性且作用机理不同于拟除虫菊酯类(使线粒体中的氧化磷酸化解偶联，线粒体电子传输抑制剂，METI)(例如参见R.N′Guessan等，ActaTropica102(2007)69-78；F.W.Mosha等，TropicalMedicineandInternationalHealth13(5)2008644-652；R.N′Guessan等，TropicalMedicineandInternationalHealth14(4)(2009)1-7)。在上述文献中也提出了氟唑虫清与拟除虫菊酯类的组合。
使用活性化合物组合时的问题在于所用杀虫剂的总量通常显著增加，出于经济学、生态学和毒理学原因，这通常是不希望的。
现已发现氟唑虫清与某些拟除虫菊酯类组合不仅使得显著降低氟唑虫清的量，而且显著降低所用拟除虫菊酯类的量(相比于使用纯活性化合物)，而不降低活性，包括对耐受拟除虫菊酯类的有害昆虫的活性。
这可能是未预料到的，因为氟唑虫清表现出较低的击昏效应，然而，该效应对于抗疟疾特别重要。只有快速麻痹才能确保蚊虫不能再叮咬并由此可能的话不能再传播疾病。惊人的是，即使拟除虫菊酯类的量相对于其单独施用而显著降低仍保持该效应。这甚至适用于具有耐受拟除虫菊酯类的特征的昆虫。
因此，本发明涉及一种用包含以下组分的杀虫混合物涂装的片状结构：
a)氟唑虫清，和
b)一种或多种选自甲体氯氰菊酯(alpha-cypermethrin)(b1)、溴氰菊酯(deltamethrin)(b2)、氯菊酯(permethrin)(b3)和氯氟氰菊酯(lambda-cyhalothrin)(b4)的拟除虫菊酯类，
其量(在每种情况下相对于片状结构)为：
a)50-150mg/m2氟唑虫清；
b1)50-150mg/m2甲体氯氰菊酯；
b2)15-45mg/m2溴氰菊酯；
b3)50-750mg/m2氯菊酯；
b4)5-30mg/m2氯氟氰菊酯。
此外，本发明涉及本发明片状结构在保护人类和家养动物免于有害昆虫和媒介传播性疾病中的用途。
本发明同样涉及防治有害昆虫以及保护人类和家养动物免于有害昆虫和/或媒介传播性疾病的方法，在所述方法中，将本发明的片状结构施用于建筑物中。
本发明的片状结构的特征在于制造简单且使用简单，尤其是呈网形式。本发明的网甚至在反复洗涤后也具有良好的杀虫活性，包括对耐受拟除虫菊酯类的有害昆虫的良好杀虫活性。所述杀虫片状结构的特征在于具有有利的毒理学数据且允许有效防治有害昆虫，包括耐受拟除虫菊酯类的有害昆虫。
杀虫剂
根据本发明，使用包含氟唑虫清与至少一种所述拟除虫菊酯类，优选基本由其组成，特别是由其组成的混合物。
氟唑虫清(1)
(IUPAC名称：4-溴-2-(4-氯苯基)-1-乙氧基甲基(5-三氟甲基吡咯-3-甲腈))可购自BASFSE且例如描述于：C.D.S.Tomlin(编辑)，ThePesticideManual，第14版，BritishCropProtectionCouncil，Alton(UK)2006中。
作为拟除虫菊酯类，使用甲体氯氰菊酯、溴氰菊酯、氯菊酯和/或氯氟氰菊酯。
尤其优选甲体氯氰菊酯、溴氰菊酯和氯菊酯。
非常特别优选甲体氯氰菊酯。
优选使用氟唑虫清与所述拟除虫菊酯类之一的二元混合物，但也可使用氟唑虫清与多种，优选两种拟除虫菊酯类的混合物。
所述活性化合物为已知的且可商购获得的；例如，氟唑虫清与甲体氯氰菊酯可由BASFSE，Ludwigshafen，德国商购获得。活性化合物例如描述于PesticideManual(参见上文)中。
每平方米片状结构的杀虫剂量通常和优选如下：
氟唑虫清(a)：50-150mg/m2，优选70-130mg/m2，尤其优选90-110mg/m2；
甲体氯氰菊酯：50-150mg/m2，优选70-130mg/m2，尤其优选90-110mg/m2；
溴氰菊酯：15-45mg/m2，优选20-40mg/m2，尤其优选25-35mg/m2；
氯菊酯：50-750mg/m2，优选75-650mg/m2，尤其优选100-550mg/m2；
氯氟氰菊酯：5-30mg/m2，优选7.5-25mg/m2，尤其优选10-20mg/m2。
因此，氟唑虫清∶拟除虫菊酯类的混合比取决于活性化合物通常为0.06-30∶1，优选0.1-10∶1，尤其优选0.1-5∶1。
杀虫剂在含水配制剂中的粒度通常为50nm至20μm，优选50nm至8μm，尤其优选50nm至4μm，尤其为50-500nm。
片状结构
合适片状结构的实例为纺织材料、非纺织塑料材料、纸、皮革、人造皮革、膜及其他(优选柔性)材料。
所用片状结构优选呈纺织材料，尤其是由纺织纤维制得的网形式。其可呈由天然纤维或合成纤维制得的网形式。当然，其也可呈两种或更多种不同纤维的混合物形式。天然纤维的实例包括棉纤维、黄麻纤维或亚麻纤维。其优选呈由合适聚合物制得的合成纤维形式。其实例包括聚酰胺、聚酯、聚丙烯腈或聚烯烃。其优选呈聚酰胺、聚烯烃和聚酯形式，尤其优选呈聚烯烃(尤其是聚丙烯或聚乙烯)和聚酯形式。非常特别优选为聚酯纤维，尤其是聚对苯二甲酸乙二醇酯(PET)。
所述纤维可呈单丝、寡丝或复丝形式，其可为光滑的或织构化的。
聚丙烯和聚乙烯可呈聚丙烯或聚乙烯均聚物形式。然而，其也可呈共聚物形式，所述共聚物包含除乙烯或丙烯以外的少量其他共聚单体。合适的共聚单体可尤其呈其他烯烃形式，所述其他烯烃例如为乙烯或丙烯和丁-1-烯、丁-2-烯、异丁烯、戊-1-烯、己-1-烯、庚-1-烯、辛-1-烯、苯乙烯或α-甲基苯乙烯、二烯烃和/或多烯烃。一般而言，聚乙烯或聚丙烯中的共聚单体总计不超过20重量％，优选不超过10重量％。本领域熟练技术人员根据所期望的纤维性质选择共聚单体的性质和用量。
对纤维制造而言，尤其优选的产品为具有较高分子量的粘性产品，其特征通常在于其熔体流动指数(如ISO1133所述测定)。优选其可呈至少一种熔体流动指数MFR(230℃，2.16kg)为0.1-60g/10分钟的聚丙烯或聚乙烯的形式。优选其呈熔体流动指数MFR(230℃，2.16kg)为1-50g/10分钟，尤其优选10-45g/10分钟，例如30-40g/10分钟的聚丙烯形式。这类聚丙烯尤其适于制造纤维。当然，也可采用多种不同类型的聚丙烯的混合物。
取决于网的性质，纺织纤维的厚度为0.05-0.6mm，优选0.1-0.4mm，尤其优选0.12-0.35mm，非常特别优选0.2-0.3mm。
纺织材料例如以覆盖物或罩形式使用，例如床罩、床垫、枕头、帘、壁纸、地毯、窗帘、橱柜及门、天花板、防水油布和篷帐布。优选网，尤其是蚊帐，例如用于起抵御蚊虫和其他有害昆虫的保护作用的床用蚊帐。
所用的优选网优选具有存在偶数个角的网目图案。就此而言，所述网可优选仅由简单类型的网目构成，例如仅由四边形网目或仅由六边形网目构成，或者其也可包含两种或更多种不同网目，例如八边形与四边形网目的组合。
就此而言，所述网的网目应优选为基本相同的类型，即尽管实际上所述网的网目形状和尺寸方面可能存在微小偏差，但数值不会过度偏离平均值。
合适的网目尺寸(正方形网目的边长)处于以5mm，优选2.5mm，尤其是1.5mm作为上限，以0.1mm，优选0.25mm，尤其优选0.5mm，尤其是0.7mm作为下限的范围内。
所述网的网目优选选自四边形、六边形或八边形网目。
四边形网目呈具有边a和b的平行四边形的网目形式。当然，术语“平行四边形”也包括术语“矩形”和“正方形”。介于平行四边形两条边之间的较小角通常为60-90°。在90°的临界情况下，平行四边形呈矩形形式。在a＝b且90°的临界情况下，其呈正方形形式。此外，平行四边形具有高ha。在矩形或正方形的情况下，高ha对应于边a的长度。特别优选正方形网目。
在六边形网目的情况下，三对边a、b和c在每种情况下均彼此平行，且以距离ha、hb和hc排列。在八边形网目的情况下，四对边a、b、c和d在每种情况下均彼此平行，且以距离ha、hb、hc和hd排列。本领域熟练技术人员知晓八边形不能获得连续图案。因此，包含八边形网目的网还额外包含至少一种第二类型的网目。这些网目可呈四边形网目形式。
在本发明的特定实施方案中，平行四边形、六边形和八边形的高ha为0.1-0.99mm，优选0.1-0.9mm，尤其优选0.12-0.8mm，非常特别优选0.25-0.7mm。
在平行四边形中，长高比b/ha为1∶1-5∶1，优选1∶1-4∶1，尤其优选2∶1-4∶1。因此，在b/ha之比为1∶1的情况下，网目可呈边长为0.1-0.99mm的正方形形式。在b/ha的较宽比情况下，其呈沿一个轴伸长的结构形式。借助不超过0.99mm的距离ha可有效地防止甚至较小昆虫穿过网，而长度实际上可大于0.99mm，以使得不会过度妨碍网的透气性。
在六边形的情况下，((hb+hc)/2)/ha比值为1∶1-5∶1，优选1∶1-4∶1，尤其优选2∶1-4∶1。此时，该情况与平行四边形类似。1∶1的比值获得具有三对等边的正六边形，其中每对等边彼此之间具有不超过0.99mm的相等距离。更大的((hb+hc)/2)/ha比值获得沿一个轴伸长的六边形。与昆虫和空气透过性有关的效果与平行四边形的情况相同。
在八边形的情况下，((hb+hc+hd)/3)/ha比值为1∶1-5∶1，优选1∶1-4∶1，尤其优选2∶1-4∶1。此时，该比例与平行四边形类似。1∶1的比值获得具有四对等边的正八边形，其中每对等边彼此之间具有不超过0.99mm的相等距离。更大的((hb+hc+hd)/3)/ha比值获得沿一个轴伸长的八边形。与昆虫和空气透过性有关的效果与平行四边形的情况相同。
除四边形和六边形网目之外，在该实施方案中也可采用例如四边形与八边形网目的组合，或改变部分网中网目的形状和尺寸。例如，可将所述网的边缘编织更加紧密，或者可以以一定距离织入也由不同聚合物制得的较厚纺织纤维以使网稳定。
术语“高”和“长”是指各网目的开孔区域，其中不考虑纤维或涂布纤维。类似地，就本发明而言，术语“网目尺寸”意指网目的孔径，即各网目的开孔区域，其中不考虑纤维或涂布纤维。
本发明该实施方案的纺织网材料描述于欧洲专利申请08161456.2中。
本领域熟练技术人员根据所需网的性质选择用于生产本发明纺织材料，尤其是本发明网的纤维的厚度。通常纤维越厚，则网的机械稳定性就越高；另一方面，与纤维覆盖区域的比例相比，开孔区域的比例随网目尺寸的减小而降低。通常纤维厚度应使得网的开孔区域占网的至少20％，优选至少40％，尤其优选至少50％。上述类型的网可商购获得。
所用网可优选呈单层网形式。然而，其也可呈称作间隔织物的形式，其中两个网借助单独的纱线彼此连接以形成双层。
涂装
术语“涂装”是指根据本发明用杀虫剂混合物对片状结构进行任意类型的处理，借助该处理实现该混合物在片状结构上或在片状结构中的均匀分布。就此而言，均匀是指某一杀虫剂的浓度在区域的任一点处基本相同。
在一个实施方案中，涂装通过用杀虫剂混合物以及粘合剂涂布片状结构或优选产生片状结构的单丝或复丝或纤维进行(方案A)。
在另一实施方案中，涂装通过如下进行：将杀虫剂混合物混合至聚合物中并将聚合物和杀虫剂混合物共挤出以得到单丝，加工单丝以得到本发明片状结构(方案B)。
通过用包含杀虫剂混合物的粘合剂涂布而涂装(方案A)
粘合剂的功能是将杀虫剂混合物固定于产生片状结构的单丝或复丝或纤维上或固定于成品片状结构(“线涂成品”)上(下文参照网描述)。由此获得的结果在于活性化合物不能浸出或至少仅非常缓慢地浸出。
聚合物粘合剂原则上可以呈任何粘合剂的形式，条件是所述粘合剂尤其能够将杀虫剂混合物固定于纺织材料上。由此优选的粘合剂为由纺织涂装和纺织涂布领域已知的那些。当然还可以使用多种不同粘合剂的混合物。
实例包括包含(甲基)丙烯酸酯的均聚物或共聚物，或聚氨酯，聚异氰脲酸酯或蜡如聚乙烯蜡。
例如，它们可以为可通过聚合乙烯属不饱和单体，优选至少一种选自如下物质的单体而获得：(甲基)丙烯酸酯，尤其是(甲基)丙烯酸的C1-至C12-酯，具有交联基团的(甲基)丙烯酸酯，(甲基)丙烯酸，马来酸或马来酸酯，丙烯腈，苯乙烯，乙酸乙烯酯，乙烯醇，乙烯，丙烯，烯丙醇或氯乙烯。
在本发明的优选实施方案中，这为乙烯属不饱和单体的共聚物，其包含如下物质作为单体：50-95重量％至少一种通式H2C＝CHR1-COOR2的(甲基)丙烯酸酯(A)，其中R1为H或甲基且R2为具有1-12个，优选2-10个碳原子的脂族直链或支化烃基。R1优选为H。合适基团R2的实例尤其包括甲基、乙基、正丁基或2-乙基己基，优选乙基、正丁基或2-乙基己基。此外，该共聚物包含1-20重量％(甲基)丙烯酸或具有另外官能团的(甲基)丙烯酸衍生物(B)。其尤其可以呈(甲基)丙烯酸酯和/或(甲基)丙烯酰胺的形式。官能团用于将粘合剂与网结合并可以另外用于交联。例如，其可以呈以下形式：(甲基)丙烯酸ω-羟烷基酯，具有环氧基团的(甲基)丙烯酸酯，例如缩水甘油酯，(甲基)丙烯酰胺或其衍生物，例如式H2C＝CH(CH3)-CO-HN-CH2-OH的(甲基)丙烯酸羟甲基酰胺。同时可以使用不同于A和B的其他乙烯属不饱和，优选单乙烯属不饱和单体(C)，例如丙烯腈或苯乙烯。其他单体的量通常为0-30重量％。尤其优选如下的粘合剂：包含70-90重量％式H2C＝CH2-COOR2的丙烯酸酯，其中R2包含4-8个C原子且优选为正丁基和/或2-乙基己基，以及另外10-20重量％丙烯腈，1-10重量％(甲基)丙烯酸或具有官能团的(甲基)丙烯酸衍生物，尤其是(甲基)丙烯酸羟甲基酰胺。
上述优选粘合剂可优选通过本领域熟练技术人员已知的方法制备，优选借助乳液聚合制备。优选丙烯酸酯粘合剂，特别是共聚物可通过乳液聚合组分B1-B4以及任选的B5而获得。
作为组分B1，使用一种或多种，优选1、2或3种，尤其优选1种式(I)的(甲基)丙烯酸酯：
H2C＝CR1-COOR2(I)
其中各符号具有如下含义：
R1为H或CH3，优选H，且
R2为C1-C10烷基，优选甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、仲戊基、新戊基、1，2-二甲基丙基、异戊基、正己基、异己基、正庚基、正辛基、2-乙基己基、正壬基或正癸基，尤其优选甲基、乙基、正丁基或2-乙基己基，非常特别优选乙基、正丁基或2-乙基己基。
作为组分B1，优选丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯和甲基丙烯酸甲酯。还优选丙烯酸丁酯自身或其与甲基丙烯酸甲酯或丙烯酸乙酯的混合物。尤其优选丙烯酸正丁酯。
用作组分B2的物质为至少一种选自如下组的单体：N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N，N′-双羟甲基马来二酰胺和N，N′-双羟甲基富马二酰胺。
优选N-羟甲基丙烯酰胺和N-羟甲基甲基丙烯酰胺，尤其为N-羟甲基甲基丙烯酰胺。
用作组分B3的物质为选自如下组的一种或多种单体，优选一种或两种单体：丙烯酸、甲基丙烯酸、乙烯基磺酸、马来酸和富马酸。优选丙烯酸和甲基丙烯酸；尤其优选丙烯酸。
用作组分B4的物质为选自B4A和/或B4B组的一种或多种单体，优选一种或两种单体。
B4A组单体为式(II)和/或(III)的那些：
H2C＝CR3X(II)ZHC＝CHZ(III)
其中各符号具有以下含义：
R3为H或CH3，优选为H；
X为Z、-CO-NH-CH2-NH-CO-CR3＝CH2或COO-CH2-CO-CH2-COOR4，优选为Z；
Z等于CONH2、CONH-CH2-OR5、COO-Y-OH、COO-缩水甘油基、CHO、CO-Y-OH，优选为CONH2；
Y为C1-C8亚烷基，优选为C2-C6亚烷基，且
R4、R5相同或不同且为直链或支化C1-C10烷基；
以及(甲基)丙烯酸系物改性的二苯甲酮类，例如如EP-A0346734所述。
作为选自B4A组的单体，优选为丙烯酸乙酰乙酰基酯、甲基丙烯酸乙酰乙酰基酯、丙烯酰胺、甲基丙烯酰胺、马来二酰胺、N-甲氧基甲基丙烯酰胺、N-正丁氧基甲基丙烯酰胺、丙烯酸3-羟丙酯、甲基丙烯酸3-羟丙酯、丙烯酸4-羟丁酯、甲基丙烯酸4-羟丁酯、丙烯酸6-羟己酯、甲基丙烯酸6-羟己酯、丙烯酸2-羟基-3-氯丙酯、甲基丙烯酸3-羟基-3-氯丙酯、丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯。尤其优选丙烯酰胺、甲基丙烯酸3-羟丙酯、丁二醇单丙烯酸酯乙酰乙酸酯、甲基丙烯酸缩水甘油酯和4-丙烯酰氧基二苯甲酮。
用作选自B4B组的单体的物质为丙烯酸烯丙基酯、丙烯酸甲基烯丙基酯、甲基丙烯酸烯丙基酯、甲基丙烯酸甲基烯丙基酯、马来酸二烯丙基酯、马来酸二甲基烯丙基酯、富马酸烯丙基酯、富马酸甲基烯丙基酯、邻苯二甲酸二烯丙基酯、邻苯二甲酸二甲基烯丙基酯、对苯二甲酸二烯丙基酯、对苯二甲酸二甲基烯丙基酯、对二乙烯基苯、丁-1，4-二醇二烯丙基醚和丁-1，4-二醇二甲基烯丙基醚。
B4组的优选单体为B4A组的那些，优选使用选自该组的一种或两种单体。
B5组的优选单体为B5A组的那些以及B5B组的乙烯基芳族单体。
优选使用丙烯腈或甲基丙烯腈，优选丙烯腈作为组分B5A。
作为组分B5B，优选苯乙烯和α-甲基苯乙烯，其中尤其优选苯乙烯。
在优选实施方案中，采用丙烯腈作为组分B5的单体以制备所述丙烯酸酯粘合剂。
丙烯酸酯粘合剂(B)可通过乳液聚合如下物质而获得(在每种情况下，以重量％表示的数据均基于B的总量)：
b1)20-93重量％，优选50-90重量％，尤其优选60-90重量％，尤其是75-85重量％的组分B1；
b2)1-5重量％，优选1.5-3重量％的组分B2；
b3)0.2-5重量％，优选0.5-4重量％，尤其优选0.75-4重量％，尤其是1-3重量％的组分B3；
b4)0-7重量％，优选0-5重量％，尤其优选0-4.5重量％，尤其是0或0.2-4.5重量％的组分B4；和
b5)0-40重量％，优选5-40重量％，尤其优选5-30重量％，尤其是0或5-26重量％的组分B5。
合适方法是本领域熟练技术人员所已知的且例如描述于WO2005/064072(第20页第20行至第23页第15行)中。
所得非交联乳液聚合物的重均分子量通常为40000-250000(由GPC(凝胶渗透色谱法)测定)。分子量通常通过使用常规用量的链终止剂，例如有机硫化合物调节。
尤其优选的丙烯酸酯粘合剂通常以含水分散体形式获得且通常以此形式用于本发明杀虫配制剂中。
优选的丙烯酸酯粘合剂可进一步包含本领域熟练技术人员已知的常规添加剂，例如成膜剂和/或增塑剂，如己二酸酯、邻苯二甲酸酯、丁基二甘醇、可通过使二羧酸与直链或支化醇反应而获得的二酯混合物。合适的二羧酸和醇是本领域熟练技术人员所已知的。
除上述粘合剂外合适的其他粘合剂为硅油和有机硅-石蜡，聚硅氧烷，具有氟化烃基的树脂，蜜胺/甲醛缩合物，羟甲基脲衍生物和可固化聚酯，其中优选硅油。
优选的硅油和有机硅-石蜡通常呈直链或环状聚硅氧烷，优选聚烷基-和/或聚苯基硅氧烷的形式，其中烷基例如为甲基、乙基、丙基或辛基，优选甲基。特别优选聚二甲基硅氧烷、聚(甲基苯基硅氧烷)和其中一定比例的甲基被高级烷基替代的相应化合物。分子量优选为1000-150000。合适的话，硅油以及尤其是有机硅-石蜡可以包含稠度调节剂如金属皂(例如硬脂酸锂)、高分散性二氧化硅、PTFE、氮化硼或脲，以获得糊状或脂肪稠度。
为了制备本发明片状结构，尤其是网，所述粘合剂可以以处于溶剂中的配制剂形式，优选含水配制剂形式应用。然而，本发明还包括使用无溶剂配制剂。
在优选实施方案中，使用包含以下物质的含水配制剂：55-99重量％的水，优选85-98重量％的水和1-45重量％，优选2-15重量％的固体，所给量在每种情况下均基于配制剂中所有组分的总量。精确浓度也取决于纺织基材的吸附性。
所述固体呈以下形式：至少一种粘合剂、杀虫混合物、任选的至少一种交联剂和任选的其他组分。
优选使用至少一种水分散性交联剂。尤其在优选的丙烯酸酯粘合剂的情况下，这优选可呈具有游离异氰酸酯基的交联剂形式。这些交联剂优选呈具有游离异氰酸酯基的异氰脲酸酯形式，优选呈衍生自具有4-12个碳原子的脂族、脂环族或芳族二异氰酸酯的异氰脲酸酯形式。其实例包括1，6-六亚甲基二异氰酸酯、1，12-十二烷二异氰酸酯、2，2’-及2，4’-二环己基甲烷二异氰酸酯或2，4-甲苯二异氰酸酯。优选基于1，6-六亚甲基二异氰酸酯的异氰脲酸酯。尤其优选具有额外的亲水基团，例如尤其是聚氧化乙烯基团的异氰脲酸酯。这类异氰脲酸酯的制备是本领域熟练技术人员所已知的。其优选以在极性非质子溶剂如碳酸亚乙酯或碳酸亚丙酯中的溶液形式使用。具有异氰酸酯基的优选交联剂的其他细节公开于WO2008/052913第34页第6行至第35页第3行中。尤其优选使用基于1，6-六亚甲基二异氰酸酯(HMDI)且具有额外的聚氧化乙烯基团的异氰脲酸酯，所述异氰脲酸酯溶于碳酸亚丙酯中(70重量％的HMDI，于碳酸亚丙酯中)。游离异氰酸酯基占该溶液的约11-12重量％。优选使用基于该配制剂的所有固体的量为1-10重量％的交联剂。异氰脲酸酯基交联剂尤其适用于交联上述共聚物。
所述配制剂可进一步包含典型的添加剂和助剂、UV稳定剂和着色剂。这些添加剂的实例描述于WO2008/052913第35页第17行至第37页第5行中。
除单纯用于美观目的之外，着色剂和颜料例如可对鸟类或哺乳动物具有警示作用，或可使杀虫网具有对昆虫的伪装效果。此外，深色可形成遮蔽，这可能是希望的且在户外应用时可降低UV光对活性化合物及纺织纤维的有害作用。
可采用交联剂和增稠剂以使处理液能均匀涂布仅可勉强润湿且因此无法均匀涂布的片状结构，例如聚烯烃纤维。为此，也可采用水溶混性溶剂，然而由于其可能对环境具有有害作用而不优选。本领域熟练技术人员熟知通常所用的助剂及其浓度。
所述配制剂优选可包含抗氧化剂、过氧化物清除剂、UV吸收剂和光稳定剂。在户外或温室中暴露于升高的UV辐照的网的情况下，这是特别推荐的。上述添加剂不仅保护基材纤维，而且也保护活性化合物免于因辐照而分解。
合适的UV吸收剂例如描述于WO02/46503或WO2007/077101中。UV吸收剂首先可用作涂装用配制剂中的组分；其次，其也可早在纤维生产过程中掺入，例如在聚烯烃和聚酯的情况下。也可有利地使用多种具有不同保护作用的稳定剂的混合物。通常，使用基于未处理网重量为0.2-5重量％，优选0.25-4重量％，非常特别优选0.5-3.5重量％的稳定剂。本领域熟练技术人员可调节配制剂中的量以适于手头任务。
根据方案B通过将杀虫剂混合物掺入单丝中而涂装
在本发明另一实施方案中，涂装通过直接将本发明混合物掺入单丝中而进行，单丝例如被加工得到组成本发明片状结构或在其中存在的纤维。在该方案中片状结构优选为网。
本发明混合物可掺入其中的单丝的合适聚合物材料为热塑性聚合物，优选基于烯属不饱和单体的那些，例如聚烯烃、聚氯乙烯、聚乙烯醇、聚(甲基)丙烯酸酯以及聚酯和聚碳酸酯，以及合适的话上述聚合物相互的混合物或与热塑性弹性体的混合物。尤其优选聚乙烯，例如低密度聚乙烯(LDPE)，例如直链低密度聚乙烯(LLDPE)，超低密度聚乙烯(ULDPE)，中密度聚乙烯(MDPE)和高密度聚乙烯(HDPE)，聚乙烯树脂，例如乙烯与具有至少3个碳原子的α-烯烃的共聚物，聚丙烯均聚物，丙烯与具有4个及更多个碳原子的α-烯烃的无规共聚物和嵌段共聚物，乙烯与不饱和羧酸化合物的共聚物，例如聚(乙烯/甲基丙烯酸甲酯)、聚(乙烯/乙酸乙烯酯)或聚(乙烯/丙烯酸)，以及该类聚合物和共聚物的混合物。热塑性弹性体的实例包括烯烃-和苯乙烯基热塑性弹性体。优选具有作为主要组分的乙烯或丙烯的共聚物，以及包含聚苯乙烯和聚异戊二烯和/或聚丁二烯嵌段的嵌段共聚物和该类共聚物的氢化衍生物。
为了生产在热塑性聚合物基质中包含本发明杀虫剂混合物的单丝，可以通过熔融捏合而混合杀虫剂混合物和聚合物。也可以首先通过熔融捏合合适量的杀虫剂混合物和聚合物而制备母炼胶，随后将该母炼胶通过再与一定量的聚合物熔融捏合而稀释至所需浓度。如果使用母炼胶方法，则对于母炼胶和随后稀释也可以使用不同聚合物，例如LLDPE用于母炼胶及HDPE用于稀释母炼胶。
除了聚合物及本发明杀虫剂混合物外，聚合物组合物合适的话包含粉状载体材料，优选选自滑石、高岭土、壤土、细粉状SiO2、碳和糊精。如果存在粉状载体材料，则其量优选为0.01-10重量％。粉状载体材料可以通过熔融捏合与杀虫剂混合物和聚合物混合，但优选首先将杀虫剂混合物与粉状材料混合并且随后将该混合物与聚合物混合，例如通过熔融捏合。尤其优选使用粉状材料与杀虫剂混合物的混合物制备母炼胶。
除了聚合物、杀虫剂混合物和合适的话粉状载体外，聚合物组合物合适的话包含对于热塑性模塑组合物常规的添加剂，例如颜料、抗氧化剂、润滑剂等。
为了生产根据本发明这些实施方案的细丝，例如优选在升高的温度下由聚合物、杀虫剂混合物和合适的话其他添加剂通过熔融捏合而制备混合物，将该混合物挤出并将挤出物加工成粒料。可通过熔融纺丝，通过挤出方法牵拉该粒料而得到细丝，本发明的网可以例如通过Raschel方法由该细丝织成。
关于本发明该实施方案的织网材料及其生产的细节例如描述于WO2008/004711中。
本发明片状结构的性质和用途
本发明片状结构，尤其是网适于保护人类和家养动物免于有害昆虫和由所述有害昆虫传播的媒介传播性疾病。
本发明片状结构也适于防治有害昆虫，其中在建筑物中施用优选呈网形式的本发明片状结构。在本发明方法的优选实施方案中，在作为食物的潜在来源吸引有害昆虫的生物或非生物体周围施用本发明的柔性片状结构，尤其是网。
根据本发明，术语有害昆虫不仅包括昆虫本身，而且包括有害蜘蛛类动物(蛛形纲(Arachnida))，尤其是作为媒介可传播疾病的那些。
本发明片状结构尤其适于抵御或防治以下目的卫生害虫和储存产品害虫：双翅目(Diptera)、蚤目(Siphonaptera)、蜚蠊目(Blattaria)(蟑螂)、革翅目(Dermaptera)、半翅目(Hemiptera)、膜翅目(Hymenoptera)、直翅目(Orthoptera)、等翅目(Isoptera)、缨尾目(Thysanura)、毛虱目(Phthiaraptera)、蜘蛛目(Araneida)和蜱螨目(Acarina)，以及唇足纲(Chilopoda)和倍足纲(Diplopoda)。它们优选适于防治双翅目、半翅目、膜翅目、蜱螨目和蚤目。
它们尤其适于防治双翅目，如蚊科(Culicidae)、蚋科(Simuliidae)、蠓科(Ceratopogonidae)、虻科(Tabanidae)、蝇科(Muscidae)、丽蝇科(Calliphoridae)、狂蝇科(Oestridae)、麻蝇科(Sarcophagidae)、虱蝇科(Hippoboscidae)、蚤目(蚤科(Pulicidae)、棒蚤科(Rhopalopsyllidae)、角叶蚤科(Ceratophyllidae))和蜱螨目(硬蜱科(Ixodidae)、软蜱料(Argasidae)、纳蜱科(Nuttalliellidae))，尤其适于防治蚊和蝇类。
本发明基材尤其适于防治：
百足虫(唇足纲)，例如家蚰蜒(Scutigeracoleoptrata)；
千足虫(倍足纲)，例如山蛰属(Narceusspp.)；
蜘蛛(蜘蛛目(Araneae))，例如黑寡妇球腹蛛(Latrodectusmactans)和褐丝蛛(Loxoscelesreclusa)；
螨(粉螨亚目(Acaridida))，例如疥螨属(Sarcoptessp.)；
寄生性螨(寄螨目(Parasitiformes))：蜱(蜱亚目(Ixodida))，例如黑脚硬蜱(Ixodesscapularis)、全环硬蜱(Ixodesholocyclus)、太平洋硬蜱(Ixodespacificus)、血红扇头蜱(Rhiphicephalussanguineus)、安氏革蜱(Dermacentorandersoni)、变异革蜱(Dermacentorvariabilis)、美洲钝眼蜱(Amblyommaamericanum)、斑点钝眼蜱(Ambryommamaculatum)、赫姆纯缘蜱(Ornithodorushermsi)、回归热蜱(Ornithodorusturicata)和中气门亚目(Mesostigmata)，例如柏氏禽刺螨(Ornithonyssusbacoti)和鸡皮刺螨(Dermanyssusgallinae)；
白蚁(等翅目)，例如黄颈木白蚁(Calotermesflavicollis)、Leucotermesflavipes、金黄异白蚁(Heterotermesaureus)、黄肢散白蚁(Reticulitermesflavipes)、美小黑散白蚁(Reticulitermesvirginicus)、欧洲散白蚁(Reticulitermeslucifugus)、Termesnatalensis和台湾乳白蚁(Coptotermesformosanus)；
蟑螂(蜚蠊目)，例如德国小蠊(Blattellagermanica)、亚洲蟑螂(Blattellaasahinae)、美洲大蠊(Periplanetaamericana)、日本大蠊(Periplanetajaponica)、棕色大蠊(Periplanetabrunnea)、黑胸大蠊(Periplanetafuligginosa)、澳洲蜚蠊(Periplanetaaustralasiae)和东方蜚蠊(Blattaorientalis)；
双翅目昆虫(双翅目)，例如蝇和蚊，例如埃及伊蚊(Aedesaegypti)、白纹伊蚊(Aedesalbopictus)、剌扰伊蚊(Aedesvexans)、墨西哥果蝇(Anastrephaludens)、五斑按蚊(Anophelesmaculipennis)、灾难按蚊(Anophelescrucians)、白端按蚊(Anophelesalbimanus)、冈比亚按蚊(Anophelesgambiae)、五斑按蚊弗氏变种(Anophelesfreeborni)、海南岛白踝按蚊(Anophelesleucosphyrus)、云南微小按蚊(Anophelesminimus)、四斑按蚊(Anophelesquadrimaculatus)、红头丽蝇(Calliphoravicina)、蛆症金蝇(Chrysomyabezziana)、螺旋金蝇(Chrysomyahominivorax)、Chrysomyamacellaria、鹿蝇(Chrysopsdiscalis)、静斑虻(Chrysopssilacea)、Chrysopsatlanticus、螺旋蝇(Cochliomyiahominivorax)、嗜人瘤蝇(Cordylobiaanthropophaga)、狂怒库蠓(Culicoidesfurens)、尖音库蚊(Culexpipiens)、斑蚊(Culexnigripalpus)、五带淡色库蚊(Culexquinquefasciatus)、媒斑蚊(Culextarsalis)、Culisetainornata、黑尾脉毛蚊(CulisetaMelanura)、人肤蝇(Dermatobiahominis)、小毛厕蝇(Fanniacanicularis)、马蝇(Gasterophilusintestinalis)、刺舌蝇(Glossinamorsitans)、须舌蝇(Glossinapalpalis)、Glossinafuscipes、胶舌蝇(Glossinatachinoides)、骚扰角蝇(Haematobiairritans)、Haplodiplosisequestris、潜蝇属(Hippelatesspp.)、纹皮蝇(Hypodermalineata)、激流细蠓(Leptoconopstorrens)、Luciliacaprina、铜绿蝇(Luciliacuprina)、丝光绿蝇(Luciliasericata)、Lycoriapectoralis、曼蚊属(Mansoniaspp.)、家蝇(Muscadomestica)、厩腐蝇(Muscinastabulans)、羊狂蝇(Oestrusovis)、银足白蛉(Phlebotomusargentipes)、哥伦比亚鳞蚊(Psorophoracolumbiae)、Psorophoradiscolor、Prosimuliummixtum、赤尾麻蝇(Sarcophagahaemorrhoidalis)、肉蝇属(Sarcophagasp.)、Simuliumvittatum、厩螫蝇(Stomoxyscalcitrans)、牛虻(Tabanusbovinus)、Tabanusatratus、红色原虻(Tabanuslineola)和Tabanussimilis；
蠼螋(革翅目(Dermaptera))，例如欧洲球螋(forficulaauricularia)；
半翅目昆虫(半翅目)，如虱和臭虫，例如温带臭虫(Cimexlectularius)、热带臭虫(Cimexhemipterus)、Reduviussenilis、锥蝽属(Triatomaspp.)、长红锥蝽(Rhodniusprolixus)和轮背猎蝽(Ariluscritatus)；
膜翅目昆虫(膜翅目)，如蚂蚁、蜜蜂、黄蜂和植物黄蜂，例如举腹蚁属(Crematogasterspp.)、樱实叶蜂(Hoplocampaminuta)、苹实叶蜂(Hoplocampatestudinea)、小黄家蚁(Monomoriumpharaonis)、热带火蚁(Solenopsisgeminata)、红火蚁(Solenopsisinvicta)、黑火蚁(Solenopsisrichteri)、南部火蚁(Solenopsisxyloni)、红蚂蚁(Pogonomyrmexbarbatus)、Pogonomyrmexcalifornicus、天鹅绒蚂蚁(Dasymutillaoccidentalis)、熊蜂属(Bombusspp.)、大黄蜂(Vespulasquamosa)、Paravespulavulgaris、Paravespulapennsylvanica、Paravespulagermanica、姬胡蜂(Dolichovespulamaculata)、黄边胡蜂(Vespacrabro)、胡蜂(Polistesrubiginosa)、佛罗里达弓背蚁(Campodontusfloridanus)和阿根廷蚁(Linepithemahumile)；
直翅目昆虫(直翅目)，如蟋蟀、蚱蜢和蝗虫，例如居屋艾蟋(Achetadomestica)、蝼蛄(Gryllotalpagryllotalpa)、飞蝗(Locustamigratoria)、双纹黑蝗(Melanoplusbivittatus)、红足黑蝗(Melanoplusfemurrubrum)、墨西哥黑蝗(Melanoplusmexicanus)、迁飞黑蝗(Melanoplussanguinipes)、石栖黑蝗(Melanoplusspretus)、条纹红蝗(Nomadacrisseptemfasciata)、美洲沙漠蝗(Schistocercaamericana)、沙漠蝗(Schistocercagregaria)、摩洛哥戟纹蝗(Dociostaurusmaroccanus)、庭疾灶螽(Tachycinesasynamorus)、塞纳加尔小车蝗(Oedaleussenegalensis)、臭腹腺蝗(Zonozerusvariegatus)、非洲蔗蝗(Hieroglyphusdaganensis)、Kraussariaangulifera、意大利蝗(Calliptamusitalicus)、澳洲草栖蝗(Chortoicetesterminifera)和褐色拟飞蝗(Locustanapardalina)；
跳蚤(蚤目)，例如猫跳蚤(Ctenocephalidesfelis)、犬跳蚤(Ctenocephalidescanis)、印鼠客蚤(Xenopsyllacheopis)、致痒蚤(Pulexirritans)、穿皮潜蚤(Tungapenetrans)和具带病蚤(Nosopsyllusfasciatus)；
衣鱼(缨尾目)，如衣鱼、家衣鱼例如西洋衣鱼(Lepismasaccharina)和斑衣鱼(Thermobiadomestica)；
虱(毛虱目)，例如人头虱(Pediculushumanuscapitis)、人体虱(Pediculushumanuscorporis)、阴虱(Pthiruspubis)、牛血虱(Haematopinuseurysternus)、猪血虱(Haematopinussuis)、牛颚虱(Linognathusvituli)、牛毛虱(Bovicolabovis)、鸡虱(Menopongallinae)、大鸡虱(Menacanthusstramineus)和牛管虱(Solenopotescapillatus)。
本发明基材尤其优选适于抵御或防治蚊(蚊科)：特别是按蚁属(Anopheles)，例如冈比亚按蚊、斯氏按蚊(AnophelesStephensi)、不吉按蚊、五斑按蚊、带棒按蚊(Anophelesclaviger)和Anophelesplumbeus；伊蚊属(Aedes)，例如埃及伊蚊(Stegomyiaaegypti)、白纹伊蚊；库蚁属(Culex)，例如五带淡色库蚊；脉毛蚊属(Culiseta)；趋血蚊属(Haemagoggus)；曼蚊属(Mansonia)；骚扰蚊亚属(Ochlerotatus)；鳞蚊属(Psorophora)；煞蚊属(Sabethes)；巨蚁属(Toxorhynchites)；Verralina；瓶草蚊属(Wyeomyia)和Zeugnomyia。
此外，本发明片状结构优选适于抵御或防治蚤目(蚤)，尤其是潜蚤属(Tunga)(沙蚤)，例如穿皮潜蚤。
本发明片状结构，尤其是网特别优选适于防治对拟除虫菊酯类或氟唑虫清、优选拟除虫菊酯类表现出抗性的有害昆虫。
除由疟原虫引起的疾病(例如热带疟疾(malariatropicana)、间日疟(malariatertiana)和三日疟(malariaquartana))以外，可防止传播的疾病也为由寄生性蠕虫引起的疾病，例如丝虫病、恶丝虫病(disofilariosis))；由病毒引起的疾病，例如黄热病、登革热、西尼罗热、基孔肯雅热(Chikungunyafever)、裂谷热(RiftValleyfever)；由细菌引起的疾病，例如兔热病(tularemia)和由寄生性单细胞生物体克鲁斯锥虫(Trypanosomacruzi)引发并由掠食性臭虫传播的查加斯病(Chagasdisease)(南美洲锥虫病)。
此外，本发明片状结构，尤其是网也适于保护待储存作物，即所收获的植物或植物部分，如果合适的话其也可呈经处理形式。
它们可通过例如将待保护的货物包裹于网中而应用。待保护的货物可呈例如木垛、水果、蔬菜、谷物、可可豆、咖啡豆或香料形式。此外，这些货物可呈大包形式。其实例包括选自茶、烟草或棉花的大包。
通过实施例更详细地阐述本发明，而非对其进行限制。
实施例
A)丙烯酸酯粘合剂
聚合物分散体的制备
一般程序
将250g水和3g平均粒度为30nm的苯乙烯Saatlatex(33重量％)加热至85℃，随后添加5重量％的进料2。10分钟后，添加进料1(参见下文)并开始添加进料2的剩余部分。
进料2包含30g溶于39.9gH2O中的过二硫酸钠。进料1的组成如表1所示。在3小时期间添加进料1和2，随后后聚合0.5小时。
表1进料1的组成(重量％pphm(份/100份单体))
基于100重量份的表1单体组合物，引发剂过二硫酸钠的量为0.3重量份，乳化剂的量为0.4重量份Dowfax2A1(Dow)和0.6重量份LumitenIRA(BASFSE)。
缩写
MMA甲基丙烯酸甲酯
S苯乙烯
AN丙烯腈
EA丙烯酸乙酯
EHA丙烯酸2-乙基己酯
BA丙烯酸正丁酯
AmolN-羟甲基丙烯酰胺
MAMolN-羟甲基甲基丙烯酰胺
AS丙烯酸
AM丙烯酰胺
Dowfax2A1：
LumitenIRA：
B)所用网的制备(用粘合剂的方案A)
表2
使用杀虫剂甲体氯氰菊酯、杀虫剂氟唑虫清、丙烯酸酯粘合剂A8和异氰酸酯基交联剂的含水配制剂涂装用于试验的各网，在大约100℃下干燥并交联1分钟。通过测定网的液体吸收量(合适的话，在给定条件下挤压后)调节表2所示杀虫剂的量，并调节配制剂的浓度，以在网上产生每平方米的所需量。调节粘合剂的量以与杀虫剂的含量匹配。
C)网的测试
如表3所示反复洗涤经处理的网。根据程序“Montpellierwashingprocedure”(如附录WHOPVC，3/07/2002“Evaluationofwashresistanceoflong-lastinginsecticidalnets”所述)进行洗涤。如WO2005/064072第46页所述实施该程序。
如WO2005/064072第47页所述，对各试样进行生物学测试。所述生物学测试对应于WHO“ConeTest”(WHOPES96.1)，其中进行微调。所测定的数据为在60分钟后的“击昏”，在24小时后的死亡。
用于试验的测试生物体首先为对拟除虫菊酯类不具有抗性的埃及伊蚊品系，其次为抗拟除虫菊酯类的冈比亚按蚊品系。
表3
| 埃及伊蚊 | 埃及伊蚊 | 冈比亚按蚊 | 冈比亚按蚊 | ||
| 洗涤 | 击昏％ | 死亡％ | 击昏％ | 死亡％ | |
| 网1 | 0 | 100 | 100 | 20 | 40 |
| 网1 | 20 | 98 | 96 | 15 | 38 |
| 网2 | 0 | 98 | 95 | 96 | 90 |
| 网2 | 20 | 100 | 100 | 100 | 85 |
| 网3 | 0 | 100 | 92 | 90 | 85 |
| 网3 | 20 | 98 | 98 | 85 | 80 |
结果证实本发明的网甚至对耐受拟除虫菊酯类的按蚊也显示出良好的效果。
Claims (17)
1.一种用包含以下组分的杀虫混合物涂装的片状结构：
a)氟唑虫清(chlorfenapyr)，和
b)一种或多种选自甲体氯氰菊酯(alpha-cypermethrin)(b1)、溴氰菊酯(deltamethrin)(b2)、氯菊酯(permethrin)(b3)和氯氟氰菊酯(lambda-cyhalothrin)(b4)的拟除虫菊酯类，
其量(在每种情况下相对于片状结构)为：
a)50-150mg/m2氟唑虫清；
b1)50-150mg/m2甲体氯氰菊酯；
b2)15-45mg/m2溴氰菊酯；
b3)50-750mg/m2氯菊酯；
b4)5-30mg/m2氯氟氰菊酯，
其中涂装为用所述杀虫剂混合物与粘合剂的混合物涂布，所得非交联乳液聚合物的重均分子量由凝胶渗透色谱法测定为40000-250000。
2.如权利要求1的片状结构，其中所述杀虫剂混合物对耐受拟除虫菊酯类的有害昆虫具有活性。
3.如权利要求1的片状结构，其中氟唑虫清的量为70-130mg/m2。
4.如权利要求1-3中任一项的片状结构，其中所述拟除虫菊酯类为甲体氯氰菊酯，其量为70-130mg/m2。
5.如权利要求1-3中任一项的片状结构，其中所述拟除虫菊酯类为溴氰菊酯，其量为20-40mg/m2。
6.如权利要求1-3中任一项的片状结构，其中所述拟除虫菊酯类为氯菊酯，其量为75-650mg/m2。
7.如权利要求1-3中任一项的片状结构，其中所述拟除虫菊酯类为氯氟氰菊酯，其量为7.5-25mg/m2。
8.如权利要求1-3中任一项的片状结构，其呈纺织材料形式。
9.如权利要求1-3中任一项的片状结构，其呈网形式。
10.一种保护人类和/或家养动物免于有害昆虫的方法，其中在人类和/或家养动物使用的建筑物中施用如权利要求1-3中任一项的片状结构。
11.一种保护人类和/或家养动物免于有害昆虫传播的媒介传播性疾病的方法，其中在人类和/或家养动物使用的建筑物中施用如权利要求1-3中任一项的片状结构。
12.一种防治建筑物中的有害昆虫的方法，其中在所述建筑物中施用如权利要求1-3中任一项的片状结构。
13.如权利要求10的方法，其中所述有害昆虫表现出拟除虫菊酯类抗性。
14.如权利要求11的方法，其中所述有害昆虫表现出拟除虫菊酯类抗性。
15.如权利要求12的方法，其中所述有害昆虫表现出拟除虫菊酯类抗性。
16.如权利要求1-3中任一项的片状结构的用途，用于防治建筑物中的有害昆虫，用于保护人类和/或家养动物免于有害昆虫和/或用于保护人类和/或家养动物免于有害昆虫传播的媒介传播性疾病。
17.如权利要求16的用途，其中所述有害昆虫表现出拟除虫菊酯类抗性。
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| PCT/EP2010/059557 WO2011003861A2 (de) | 2009-07-09 | 2010-07-05 | Insektizides flächengebilde zum schutz von menschen und haustieren |
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| EP2451283B1 (de) * | 2009-07-09 | 2017-06-21 | Basf Se | Insektizid beschichtetes substrat zum schutz von menschen und haustieren |
| EP2736319B1 (de) | 2011-07-26 | 2015-10-07 | BASF Agro B.V., Arnhem (NL), Zürich Branch | Vorrichtung zum ausbringen von flexiblen flächengebilden |
| WO2013079601A1 (en) | 2011-12-02 | 2013-06-06 | Basf Se | Method and system for monitoring crops and/or infestation of crops with harmful organismus during storage |
| WO2013079600A1 (en) | 2011-12-02 | 2013-06-06 | Basf Se | Method and system for monitoring crops during storage |
| US20130273619A1 (en) | 2012-04-16 | 2013-10-17 | Basf Se | Process for the Preparation of (3E, 7E)-Homofarnesol |
| MY182275A (en) | 2012-07-13 | 2021-01-18 | Basf Agro B V Arnhem Nl Zurich Branch | Evacuable packaging for insecticide-impregnated nets |
| EP2708126A1 (en) * | 2012-09-14 | 2014-03-19 | Aragon Net Ltd. | Insecticidal aerosol |
| JP5646016B1 (ja) * | 2013-07-29 | 2014-12-24 | 新日鐵住金ステンレス株式会社 | 害虫忌避性クリヤ塗装ステンレス鋼板及びその製造方法 |
| EP2859794B1 (en) * | 2013-10-08 | 2016-12-21 | In2Care Holding B.V. | A complex of structures for delivering pesticidal agents to arthropods |
| GB201319336D0 (en) * | 2013-11-01 | 2013-12-18 | Liverpool School Tropical Medicine | Mosquito bed net assembly |
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| CN112680962A (zh) * | 2020-12-18 | 2021-04-20 | 天津永阔科技发展有限公司 | 一种用于处理驱蚊织物的新型杀虫剂整理液及使用方法 |
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| BR112012000491A2 (pt) | 2015-10-06 |
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| US20120114727A1 (en) | 2012-05-10 |
| CO6420394A2 (es) | 2012-04-16 |
| WO2011003861A3 (de) | 2011-07-07 |
| ZA201200873B (en) | 2013-05-29 |
| JP2012532841A (ja) | 2012-12-20 |
| MX2012000334A (es) | 2012-01-30 |
| TW201105237A (en) | 2011-02-16 |
| AR077470A1 (es) | 2011-08-31 |
| KR20120052290A (ko) | 2012-05-23 |
| WO2011003861A2 (de) | 2011-01-13 |
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