CN1161017C - 增效喷雾杀虫剂组合物 - Google Patents
增效喷雾杀虫剂组合物 Download PDFInfo
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Classifications
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- 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
- A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
- A01N29/04—Halogen directly attached to a carbocyclic ring system
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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
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明提供了一种含有有效剂量杀虫剂、摩擦剂、少量表面活性剂、惰性载体和可选的成膜抑制剂的喷雾杀虫剂组合物，其效果显著加强。
Description
对蟑螂及其它爬行昆虫的防治传统防治方法是通过在屋内受其侵害的小生境中喷洒用水稀释的杀虫剂来实现的。在防治典型栖息于厨房、食品储存区等地方的德国蟑螂这类害虫时，，必须将这类杀虫剂喷洒在住所或商号的各种基材上。许多这类基材，例如颗粒板或相关组合材料、聚氯乙烯地砖或油漆的涂面，这些都是高空隙率的，能使杀虫剂吸附到这些基材中去，由此限制了活性成份的利用因而不能够针对害虫起到防治作用。
众所周知，乳化浓缩液喷雾剂很容易渗透到多孔性基材内去从而使得多孔性基材的表面却少有杀虫剂。常用杀虫剂的悬浮浓缩组合物，如芳基吡咯，尤其是虫螨腈(chlorfenapyr)，已在美国专利5,496,845中作了介绍。
本发明的目的之一是提供一种效果提高的喷雾杀虫剂组合物，尤其适用于住家、仓库、商号内各种基材的表面。
现已发现，由摩擦剂、消膜剂或残留物组成的可进行喷雾的杀虫剂组合物，特别是在应用于住家、仓库、商号场所内各类基材的表面上，经喷雾和干燥后，效果会显著增强。
本发明提供了一种喷雾杀虫剂组合物，它包含杀虫有效量的杀虫剂；摩擦剂；少量表面活性剂；惰性载体；和可选性的成膜抑制剂。在将本发明喷雾组合物喷洒与住家、仓库、商号所内各种基材的表面时，它对于爬行类昆虫害虫具有高于一般的防治效果。
美国专利5,310,938所述的芳基吡咯类杀虫剂是强效接触性杀虫剂，如果被所针对的传播性害虫所摄入，同样具有很强的昆虫胃内毒性，它是极其有效的。在作物保护实践中，喷雾杀虫剂通常是有效的，因为，目标害虫不仅会与残留杀虫剂接触，而且会在取食喷洒后的植物时将其摄入。但是，与一般的芳基吡咯杀虫剂喷雾悬浮浓缩液相比，本发明组合物出人意料地表现出更高的防治建筑物内害虫(structural pest)的效力。
令人惊奇的是，现已发现，包含有效量的杀虫剂(例如芳基吡咯)、摩擦剂、少量表面活性剂、惰性载体和可有可无的成膜抑制剂的喷雾杀虫剂组合物的对爬行昆虫类害虫(例如蟑螂、蚂蚁、蟋蟀、蠹虫、蠼螋面粉甲虫、白蚁、钻木甲虫等)表现出特别显著的防治效果。本发明组合物会形成一层不沉积(dislodegable)的摩擦性残留物，它粘着并刺激从该表面上经过或越过的爬行昆虫类害虫，这些有杀虫作用的残留粘附物可直接从表皮被吸收，这种作用在当这些目标害虫为了清除触角或跗节等身体部分上的残留而间接吞入时更显著。本发明组合物优点在于，表现出的效果优于常规杀虫剂组合物喷洒悬浮液。
任何已知用于防治爬行昆虫的杀虫剂都适合用作本发明的杀虫剂，较好的是芳基吡咯，尤其是虫螨腈。在实际操作中，杀虫有效量取决于本领域工艺上的多种因素，例如活性有效成份，较标准的是以重量/重量(wt/wt)约为10％-70％为基础，10％-30％更佳。
适合用于本发明的摩擦剂可以是硅酸盐(例如碱土金属硅酸盐或碱金属硅酸盐(以硅酸钙为佳))，或二氧化硅或高岭土或上述物质的混合物，其中以硅酸钙、二氧化硅或高岭土或它们的混合物为佳。硅酸钙更号.摩擦剂的含量较合适的是按wt/wt计算，约3％-9％，5％-7％更好。
任何已知的表面活性剂、润湿剂、分散剂或上述物质的混合物都适合作本发明组合物中的表面活性剂。表面活性剂可以是乳化剂、分散剂或润湿剂；这可以是离子型的或是非离子型的。合适的表面活性剂包括例如聚丙烯酸和木素磺酸的钠盐或钙盐；烷基化萘磺酸酯的甲醛缩合物(例如MORWETD425)；磺基琥珀酸二辛基钠；具有环氧乙烯或环氧丙烯基的至少12个碳原子的脂肪族胺或酰胺的脂肪酸缩合物；乙二醇、山梨醇、蔗糖或季戊四醇的脂肪酸酯；以上物质与环氧乙烷或环氧丙烷的缩合物；脂肪醇或烷基酚(例如对辛基苯酚或对辛基甲酚)与环氧乙烷或环氧丙烷的缩合物；上述缩合产物的硫酸盐或磺酸盐；分子中至少含10个碳原子的硫酸酯或磺酸酯的碱金属或碱土金属盐(以钠盐为佳)(例如十二烷基硫酸钠、仲烷基硫酸钠、磺化蓖麻油的钠盐、和烷基芳基磺酸(例如十二烷基苯磺酸)钠)；和环氧乙烷的聚合物和环氧乙烷和环氧丙烷的共聚物。较好的是表面活性剂包括烷基化萘磺酸钠盐和磺化琥珀酸二辛基钠。在实际操作中，在成膜抑制剂存在时，表面活性剂的水平可比所述抑制剂不存在时高。合适的表面活性剂水平(不含所述抑制剂)按wt/wt计算8％，例如2％-7％，较好的是3％-5％。在没有成膜抑制剂时，低于8％的表面活性剂水平在此称作“少量”表面活性剂。在有成膜抑制剂时，表面活性剂量可高达15％，而在8％-12％时仍可认为是少量存在。特别好的是含有成膜抑制剂而表面活性剂约低于8％的组合物。
适用于本发明组合物的惰性载体可以是任何农业上采用的固体或液体载体，以固体载体为佳.合适的固体载体包括天然或合成粘土和硅酸盐，例如硅藻土之类的天然二氧化硅；硅酸镁，例如滑石；硅酸镁铝，例如美国活性白土(attapulgites)和蛭石；硅酸铝，例如高岭土、蒙脱石和云母；碳酸钙；硫酸钙；硫酸铝；合成的水合氧化硅或合成的硅酸钙或硅酸铝；元素，例如碳和硫；天然或合成树脂，例如香豆素树脂、聚氯乙烯和苯乙烯的聚合物和共聚物。较好的固体载体是高岭粘土、硅藻土、蒙脱石粘土等，以高岭土为更佳。在实际操作中，惰性载体在本发明组合物中的含量按wt/wt计算约为25％至75％，约55％-65％更好。
在喷洒了组合物并干燥后，能够抑制形成一张连续的膜残留物的颗粒物都是适用于本发明组合物的可选的成膜抑制剂。尤其有用的是无机盐，例如碱金属卤化物和碱土金属卤化物，较好的是氯化钙之类碱土金属卤化物。组合物中有无机盐存在能够抑制残留组合物在干燥后形成一层连续的膜。但是，如果组合物中表面活性剂含量足够低，则不需要成膜抑制剂来得到不沉积的残留物。在实际操作中，如果有成膜抑制剂存在，其含量按wt/wt计算，约为1％-6％，约2％-4％更好。
本发明的喷雾杀虫剂组合物可以如下制备：将有效量的杀虫剂(例如虫螨腈)，摩擦剂(例如硅酸盐、二氧化硅、高岭土或它们的混合物，以诸如硅酸钙的硅酸盐为佳)，少量(例如少于8％wt/wt)表面活性剂，惰性载体(例如高岭土)和可选的成膜抑制剂(例如无机盐)混合并研磨直至均匀。重要的是，证实了喷雾杀虫剂具有尽可能小的吸附作用，才能在昆虫进入或越过处理区域时才会有最大的有效杀虫效果。
本发明还提供了一种防治爬行昆虫的方法，它包括在爬虫出没区域喷洒有效量的本发明组合物。所述的区域不仅限于任何爬行昆虫可能爬及的地方，还包括它们的栖息地、繁殖区。或食物来源区。
为了更清楚的理解本发明，现给出以下实施例。这些实施例只是说明性的，而绝对不能理解成是对本发明范围或所函理论的限定。
除非另作说明，所有的分数都是重量百分比。
实施例1
含有摩擦剂的喷雾杀虫剂组合物增效结果的评价
表I所示的可湿性粉末组合物由所有成份混合并研磨至均质制备而成
表I
wt/wt
成份 A B C D E F G
虫螨腈 72.0 56.6 41.1 25.7 24.8 24.8 24.8
润湿剂1 2.5 2.5 2.5 2.5 2.5 2.5 2.5
分散剂2 4.5 4.5 4.5 4.5 17.5 17.5 4.5
氯化钙 1.0 1.0 1.0 1.0 1.0 1.0 1.0
硅酸钙 - - - - 2.0 - -
高岭土 20.0 35.4 50.9 66.3 64.8 54.2 67.2
1MORWETEFW，Witco出品，Houston，TX
2MORWETD425，Witco出品，Houston，TX
在此评价中，将上述各样品分散在水中，并喷洒在一块玻璃的表面上，使得每平方米活性成份的得率为：10mg。对于每一处理，在喷洒过的玻璃表面上放上一组10个德国蟑螂(Blattela germanica)，让它们在上面停留1小时或6小时。然后将蟑螂转移到干净的罐中观测其死亡率。在处理后(DAT)的第1、2和4天观测死亡率。每一种处理重复三次。取数据的平均值，列于表II。
表II
％死亡率
第1天 第2天 第4天
测试样品 1hr. 6hr. 1hr. 6hr. 1hr. 6hr.
I-A 30 20 30 25 35 35
I-B 15 50 40 60 40 60
I-C 30 50 35 65 40 70
I-D 45 45 60 55 65 55
I-E 85 95 95 95 100 95
I-F 10 70 15 75 25 85
I-G 60 95 90 95 95 100
未处理 0 0 0 0 0 0
根据表II的数据可以看出，加入硅酸钙之类的摩擦剂(I-E)和/或大量高岭土之类摩擦剂(I-G)显著加强了本发明喷雾杀虫剂组合物的效力。而且，可以看出，高含量的表面活性剂(I-F)会减弱效果。
实施例2
含有少量表面活性剂的喷雾杀虫剂组合物效果的评价和 含有少量表面活性剂的喷雾杀虫剂组合物相对规杀虫剂组合物的比较性评价
表III所示的可湿性粉末组合物由所有成份混合并研磨至均质制备而成。
表III
wt/wt％
成份 A B C D E F G H I
虫螨腈 25.1 25.1 25.1 25.1 25.1 25.1 25.1 25.1 25.1
润湿剂1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
分散剂2 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
氯化钙 - 3.0 6.0 - 30. 6.0 - 3.0 6.0
硅酸钙 - - - 3.0 3.0 3.0 6.0 6.0 6.0
高岭土 70.9 67.9 64.9 67.9 64.9 61.9 64.9 61.9 58.9
1MORWETEFW，Witco出品，Houston，TX
2MORWETD425，Witco出品，Houston，TX
如美国专利5,496,845所述制备含22.2％wt/wt虫螨腈且基本上不含摩擦剂的浓缩悬浮液(2SC)，对其进行评价和比较将在后面述及。
在此次评价中，将上述各份样品分散在水中，并喷洒在玻璃表面上，使得每平方米上活性成份的得率为10mg。每种处理都是将一组10只德国蟑螂放在喷涂过的玻璃表面上1.25小时，然后转移到洁净的罐中。在处理后(DAT)的4日内每天观测死亡率。每一种处理重复三次。取数据的平均值，列于表IV。
表IV
％死亡率
测试样品 第1天 第2天 第3天 第4天
III-A 36.67 50.00 50.00 50.00
III-B 43.33 63.33 63.33 63.33
III-C 53.33 63.33 66.67 66.67
III-D 53.33 63.33 63.33 63.33
III-E 46.67 70.00 70.00 70.00
III-F 40.00 63.33 63.33 63.33
III-G 50.00 76.67 80.00 80.00
III-H 26.67 46.67 46.67 46.67
III-I 36.67 63.33 66.67 66.67
2SC 10.00 16.67 16.67 16.67
未处理 3.33 3.33 3.33 3.33
从表IV数据可以看出，不论是含有氯化钙(III-E)或不含氯化钙(III-G)，包含较少量的表面活性剂与较高含量的摩擦剂的喷雾杀虫剂组合物均提高了效果。而且，从表IV的数据还可以看出，与常规喷雾杀虫剂组合物(2SC)相比，本发明组合物的效果明显提高。
实施例3
本发明喷雾杀虫剂组合物的效果与常规喷雾杀虫剂组合物的比较性评价表列可湿性粉末组合物由所有成份混合并研磨至均质制备而成.
组合物A
成份 wt/wt％
虫螨腈 25.9
润湿剂1 1.5
分散剂2 2.5
氯化钙 3.0
硅酸钙 6.0
高岭土 61.1
1MORWETEFW，
2MORWETD425，
组合物B
如美国专利5,496,845所述制备含22.2％虫螨腈且基本上不含摩擦剂的浓缩悬浮液(2SC)，对其进行评价，并如下所述进行比较。
在此次评价中，将上述各份样品分散在水中，并喷洒在木纤维板(多孔性基质)或不锈钢(无孔基质)表面上，使得喷洒率为100mg/M2和200mg/M2。针对每种处理，将一组10只雄性德国蟑螂在喷涂过的表面上放置1小时，然后转移到洁净的罐中。在处理后(DAT)的第1、2和4天观测死亡率。每一种处理重复三次。取数据的平均值，列于表V。
表V
％死亡率
被测组合物 表面类型 喷洒率(mg/M2) 第1天 第2天 第4天
A 木纤维板(Masonite) 200 53 80 88
A 木纤维板(Masonite) 100 15 43 70
A 不锈钢 200 62 83 95
A 不锈钢 100 33 53 85
B 木纤维板(Masonite) 200 3 25 48
B 木纤维板(Masonite) 100 8 15 25
B 不锈钢 200 3 25 63
B 不锈钢 100 8 13 53
从表V的数据可以看出，与常规喷雾杀虫剂组合物(B)相比，本发明的喷雾杀虫剂组合物(A)对爬行昆虫的效果显著提高。两种基质，无孔性的(不锈钢)和多孔性的(木纤维板)都证明了这种效果的提高。
实施例4
本发明喷雾杀虫剂组合物对多种蟑螂的效果
与常规喷雾杀虫剂组合物的比较性评价
基本上按照实施例3的过程进行，使用乙烯基表面(空隙率相当高)喷以实施例3中的被测组合物A和B，喷洒率为100mg/M2，令三种蟑螂与表面接触1小时，然后转移到洁净的罐中。每种处理重复五次。在处理后的第1和第2天观测死亡率。取数据的平均值，列于表VI。
所用的昆虫种类
俗名 学名
美洲蟑螂 Periplaneta americana
烟色蟑螂 Periplaneta fuliginosa
东方蟑螂 Blatta orientalis
表VI
％死亡率
被测组合物 蟑螂种类 第1天 第2天
A 美洲蟑螂 100 100
A 烟色蟑螂 68 100
A 东方蟑螂 88 100
B 美洲蟑螂 0 0
B 烟色蟑螂 0 7
B 东方蟑螂 0 47
从表VI的数据可以看出，与常规喷雾组合物相比，本发明喷雾杀虫剂对各种蟑螂的效果显著提高。
实施例5
本发明喷雾杀虫剂组合物直接用于目标物种时
与常规喷雾杀虫剂组合物相比的评价
在此评价中，使用的是实施例3中所述的组合物A和B的稀释液。蟑螂栖息所有一每组德国蟑螂成虫(5个雄性5个雌性)，受其危害，人杂然后对此场所内喷以稀释后的被测组合物。每种处理重复8次。在处理后的第1小时、第1天和第4天观测死亡率。取数据的平均值，列于表VII。
表VII
％死亡率
被测组合物 浓度(wt/wt％ 第1小时 第1天 第4天
av.)
A 0.50 38 76 99
A 0.25 25 81 98
B 0.50 15 50 79
B 0.25 10 50 71
从表VII数据可以看出，在与昆虫直接接触后的效果与常规喷雾组合物(B)相比，本发明的喷雾杀虫剂组合物(A)效果显著提高。
Claims (10)
1.一种非水性喷雾杀虫剂组合物，按组合物总重计，它包含：
10-70wt％杀虫剂；
3-9wt％摩擦剂，所述摩擦剂选自碱金属硅酸盐或碱土金属硅酸盐；
2-7wt％表面活性剂；
25-75wt％固体惰性载体。
2.根据权利要求1所述的组合物，它还包含1-6wt％成膜抑制剂。
3.根据权利要求2所述的组合物，所述成膜抑制剂是碱金属卤化物或碱土金属卤化物。
4.根据权利要求1所述的组合物，其中的固体惰性载体是高岭土。
5.根据权利要求1所述的组合物，其中的摩擦剂是硅酸钙。
6.根据权利要求5所述的组合物，其中，硅酸钙的含量为组合物总重的5-7wt％。
7.根据权利要求1所述的组合物，它包含：
10-30wt％杀虫剂；
3-9wt％摩擦剂，所述摩擦剂选自碱金属硅酸盐或碱土金属硅酸盐；
2-7wt％表面活性剂；
55-75wt％固体惰性载体；和
1-6wt％成膜抑制剂。
8.根据权利要求1所述的组合物，它包含：
10-30wt％杀虫剂；
3-9wt％硅酸钙；
2-7wt％表面活性剂；
55-75wt％高岭土；和
1-6wt％氯化钙。
9.根据权利要求1所述的组合物，其中所述的杀虫剂是针对爬行昆虫的杀虫剂。
10.根据权利要求9所述的组合物，其中所述的爬行昆虫选自蟑螂、蚂蚁、蟋蟀、蠹虫、蠼螋面粉甲虫、白蚁或钻木甲虫。
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| DE (1) | DE69908848T2 (zh) |
| ES (1) | ES2203012T3 (zh) |
| HU (1) | HUP9900817A2 (zh) |
| ID (1) | ID23331A (zh) |
| NZ (1) | NZ334947A (zh) |
| SK (1) | SK32499A3 (zh) |
| ZA (1) | ZA992446B (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8298485B2 (en) | 1999-07-08 | 2012-10-30 | Lee H. Angros | In situ heat induced antigen recovery and staining apparatus and method |
| US7897106B2 (en) | 1999-07-08 | 2011-03-01 | Lee Angros | Situ heat induced antigen recovery and staining apparatus and method |
| US7951612B2 (en) | 1999-07-08 | 2011-05-31 | Lee H. Angros | In situ heat induced antigen recovery and staining apparatus and method |
| WO2001004634A1 (en) | 1999-07-08 | 2001-01-18 | Lee Angros | Antigen recovery and/or staining apparatus and method |
| EP1888739B1 (en) | 2005-05-24 | 2021-08-11 | Lee H. Angros | Automated apparatus and method for treating biological specimens on slides |
| JP4767113B2 (ja) * | 2006-07-13 | 2011-09-07 | 株式会社アムテック | シロアリ防除剤 |
| GB2477648B (en) | 2008-08-29 | 2013-02-20 | Lee H Angros | In situ heat induced antigen recovery and staining apparatus and method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58124703A (ja) * | 1982-01-20 | 1983-07-25 | Sumitomo Chem Co Ltd | 殺虫方法 |
| US4678774A (en) * | 1985-06-06 | 1987-07-07 | Merck & Co., Inc. | Novel synergistic compositions |
| US5439690A (en) * | 1993-05-21 | 1995-08-08 | Ecosmart, Inc. | Non-hazardous pest control |
| ATE189356T1 (de) * | 1994-08-19 | 2000-02-15 | Monsanto Co | Zuführung exogener chemischer substanzen an pflanzengewebe |
| GB9520033D0 (en) * | 1995-09-30 | 1995-12-06 | Insect Investigations Ltd | Weedkiller |
| GB2314774B (en) * | 1996-07-03 | 1998-09-23 | R & C Products Pty Ltd | Improvements in or relating to organic compositions |
| IL121430A (en) * | 1996-08-02 | 2002-03-10 | American Cyanamid Co | Process for the preparation of arylpyrrole particles in stable crystalline form and suspension concentrate compositions comprising stable arylpyrrole particles prepared by this process |
-
1999
- 1999-02-18 ID IDP990127D patent/ID23331A/id unknown
- 1999-03-12 SK SK324-99A patent/SK32499A3/sk unknown
- 1999-03-17 KR KR1019990008969A patent/KR100566503B1/ko not_active Expired - Fee Related
- 1999-03-25 CZ CZ991069A patent/CZ106999A3/cs unknown
- 1999-03-26 ES ES99302383T patent/ES2203012T3/es not_active Expired - Lifetime
- 1999-03-26 EP EP99302383A patent/EP0947135B1/en not_active Expired - Lifetime
- 1999-03-26 DE DE69908848T patent/DE69908848T2/de not_active Expired - Lifetime
- 1999-03-26 JP JP08409999A patent/JP4430152B2/ja not_active Expired - Fee Related
- 1999-03-26 AT AT99302383T patent/ATE242961T1/de not_active IP Right Cessation
- 1999-03-29 AU AU22499/99A patent/AU764648B2/en not_active Ceased
- 1999-03-29 BR BRPI9901347-9A patent/BR9901347B1/pt not_active IP Right Cessation
- 1999-03-29 CA CA002267135A patent/CA2267135A1/en not_active Abandoned
- 1999-03-30 AR ARP990101433A patent/AR023302A1/es active IP Right Grant
- 1999-03-30 CN CNB99104746XA patent/CN1161017C/zh not_active Expired - Fee Related
- 1999-03-30 ZA ZA9902446A patent/ZA992446B/xx unknown
- 1999-03-30 HU HU9900817A patent/HUP9900817A2/hu unknown
- 1999-03-30 NZ NZ334947A patent/NZ334947A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE69908848T2 (de) | 2004-05-13 |
| NZ334947A (en) | 2000-08-25 |
| AU2249999A (en) | 1999-10-14 |
| ES2203012T3 (es) | 2004-04-01 |
| JP4430152B2 (ja) | 2010-03-10 |
| AR023302A1 (es) | 2002-09-04 |
| HU9900817D0 (en) | 1999-05-28 |
| CA2267135A1 (en) | 1999-09-30 |
| AU764648B2 (en) | 2003-08-28 |
| SK32499A3 (en) | 1999-12-10 |
| DE69908848D1 (de) | 2003-07-24 |
| JPH11310502A (ja) | 1999-11-09 |
| EP0947135B1 (en) | 2003-06-18 |
| CN1230338A (zh) | 1999-10-06 |
| ID23331A (id) | 2000-04-05 |
| KR19990077970A (ko) | 1999-10-25 |
| ATE242961T1 (de) | 2003-07-15 |
| BR9901347B1 (pt) | 2010-12-14 |
| ZA992446B (en) | 2000-10-11 |
| BR9901347A (pt) | 2000-02-29 |
| CZ106999A3 (cs) | 1999-10-13 |
| EP0947135A1 (en) | 1999-10-06 |
| KR100566503B1 (ko) | 2006-03-31 |
| HUP9900817A2 (hu) | 2001-06-28 |
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