CN114206111B - 节肢动物驱避组合物 - Google Patents
节肢动物驱避组合物 Download PDFInfo
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- CN114206111B CN114206111B CN202080048208.4A CN202080048208A CN114206111B CN 114206111 B CN114206111 B CN 114206111B CN 202080048208 A CN202080048208 A CN 202080048208A CN 114206111 B CN114206111 B CN 114206111B
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Classifications
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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
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
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Abstract
本发明涉及一种节肢动物驱避组合物,其提供长期保护,特别是针对昆虫和蜱的长期保护。
Description
本发明涉及一种节肢动物驱避组合物,其提供长期保护,特别是针对昆虫和蜱(tick)的长期保护。
在本说明书中,术语“节肢动物(Arthropoda)”用于指昆虫纲、蛛形纲和多足纲物种,特别是昆虫纲和蛛形纲,优选任何类型的蚊和蜱。
“昆虫驱避组合物(insect repellent composition)”意指表现出驱虫效果或杀虫效果,或同时表现出驱虫效果和杀虫效果的组合物。
期望驱虫剂满足几个基本要求,例如商业可得性、低成本、无异味、被归类为无刺激性和无毒物质、高稳定性和与足够的持久有效的拒虫效果相关的可接受的(acceptable)蒸发速率。解决最后一个问题,即将驱虫剂从驱虫剂制剂(repellent formulation)中释放的速率控制在有效水平,是驱虫剂行业面临的巨大挑战。此外,已知挥发性驱虫剂(volatile insect repellent)被施用于皮肤时会相对快速地消失。例如在下雨、出汗、游泳或淋浴(showering)时,它们还很容易被水冲走。驱虫剂的蒸发与环境温度、体温和风速直接相关。
另一个挑战是,约50%的局部施用剂量在6小时内被皮肤吸收,1小时内达到血浆峰值水平(Lurie et al,Pharmacokinetics of insect repellent N,N-diethyltoluamide.Med.Parazitol.,47,72,1979)。众所周知,经常用作助溶剂(co-solvent)的乙醇会显著增加和加速活性成分渗透到皮肤中。这一方面导致皮肤表面上的活性物质的流失,另一方面可能导致皮肤刺激和过敏反应。因此,在现代配方中,醇有时至少部分地被表面活性剂取代。然而,表面活性剂的使用也隐藏了潜在的皮肤刺激或过敏反应形式的缺点。
利用物理屏障来控制驱虫剂的释放已经取得了一些进展。将挥发性驱虫剂掺入聚合物中、将挥发性驱虫剂包封在壳或壁材料(walled material)中以及使用多孔和/或层状材料作为挥发性活性载体是尝试提供控释驱虫剂制剂的实例。
使用的一种众所周知的驱虫剂是N,N’-二乙基甲基苯甲酰胺,通常称为DEET。其他挥发性驱虫剂是已知的,包括乙基己二醇;2-(辛硫基)乙醇;邻苯二甲酸二甲酯;二正丙基-2,5-吡啶二甲酸酯;1,5a,6,9,9a,9b-六氢-4a(4b)-二苯并呋喃甲醛;香茅醛;香茅醇;香叶醇;橙花醇;和芳樟醇。由于许多驱虫剂的油腻感,特别是在潮湿或多雨的天气中或当使用驱虫剂的人正在参加水上运动如游泳或钓鱼时DEET在沾染(staining)衣服、使塑料开裂以及被洗掉方面的作用,此类驱虫剂的制剂(formulation)特别成问题。此外,由于水的作用而导致的驱虫剂滞留性不足也受到个人穿戴者(wearer)出汗的影响。
Mehr等人(Laboratory Evaluation of Controlled-Release Insect RepellentFormulations,J.Am.Mosq.Control Assoc.,1,143,1985)评价了微胶囊化的DEET和亲水性乙烯基聚合物如聚乙烯吡咯烷酮的许多控释制剂。在驱蚊方面,聚乙烯吡咯烷酮配方(formula)并不比未经配制的(unformulated)DEET好。
Reifenrath等人(Evaporation and Skin penetration characteristics ofmosquito repellent formulations.J.Am.Mosq.Control Assoc.,5,45 1989)测试了硅酮聚合物、丙烯酸酯聚合物、脂肪酸和驱虫剂的混合物,并评价了蒸发特性和皮肤渗透特性。在含有聚合物的制剂和未经配制的(unformulated)DEET或与邻苯二甲酸二甲酯和DEET的混合物之间,在蒸发特性和皮肤渗透特性方面未发现差异。
EP 2439188 A1描述了将活性物质包埋在纤维素基质(cellulosic matrix)中,并且US 4,474,081公开了马来酸酐/α-烯烃聚合物和三元共聚物在被施用到皮肤表面时提供接触性驱虫剂的缓慢释放的用途。
US 4,774,082公开了马来酸酐/α-烯烃聚合物和三元共聚物在提供施用于皮肤表面的挥发性驱虫剂的缓慢释放方面的用途。
化学文摘(Chemical Abstracts)110,207847s(1989)公开了具有活性剂和油溶性、水不溶性的丙烯酸酯聚合物的驱蚊组合物(mosquito repellent composition),该丙烯酸酯聚合物包含丙烯酸、甲基丙烯酸硬脂酯和丙烯酸异辛酯。
此外,还考虑了以延长作用时间为目的的衍生化(derivatisation)。因此,例如,WO 2004/006674 A描述了PMD的Cg-so酯的生产。此外,JP 31335906 A描述了一种驱虫剂,其含有N,N-二乙基甲苯甲酰胺(N,N-diethyltoluamide,DEBT)和对薄荷烷衍生物,例如对薄荷烷-3,8-顺式二醇的一元羧酸或磺酸酯(sulphonate)。
WO 2017/199145 A描述了至少一种第一化合物和与之不同的第二化合物的组合,至少第一化合物是驱虫剂,在环境压力和温度下,第一化合物和第二化合物能够与蒸汽组合物一起形成负假共沸物(negative pseudo-azeotrope),其中第一化合物以足够高的浓度存在以提供驱虫效果。在本申请中,已经将几种已知的驱虫剂化合物进行了组合,然而,因为它们不会形成负假共沸物,已经发现它们并不合适。
WO 2018/50211A公开了一种包含驱虫剂(insect repellent)或杀虫剂(insecticide)和环糊精或环糊精衍生物的驱虫组合物,其中与所述环糊精(衍生物)相比,以明显过量的比例提供驱虫剂/杀虫剂。所述申请中所示的所有制剂均包含至少80重量%的醇含量。
本发明的目的是提供一种哺乳动物用驱虫制剂,该制剂应无刺激性、高效、不沾染(non-staining)、不油腻、稍有粘性、持久,并且平衡了驱虫化合物在皮肤中的溶解性和渗透性。
该目的通过一种节肢动物驱避组合物来实现,该组合物包含(ⅰ)埃卡瑞丁(1-(1-甲基丙氧羰基)-2-(2-羟乙基)哌啶),(ⅱ)任选地至少一种另外的节肢动物驱避化合物,该节肢动物驱避化合物选自PMD(对薄荷烷-3,8-二醇)、DEET(N,N-二乙基间甲基苯甲酰胺)、IR 3535(3-丁基乙酰氨基丙酸乙酯)(ethyl-3-acetylbutylaminopropanoate)、KBR 3023((RS)-仲丁基-(RS)-2-(2-羟乙基)哌啶-1-羧酸酯)或邻氨基苯甲酸乙酯(2-氨基苯甲酸乙酯),以及(ⅲ)选自PPG-20甲基葡萄糖醚、PPG-10甲基葡萄糖醚、丙二醇、丁二醇和戊二醇中的至少一种多元醇。
本发明涉及包含以下节肢动物驱避化合物的组合物:(ⅰ)埃卡瑞丁(1-(1-甲基丙氧羰基)-2-(2-羟乙基)哌啶)和任选地但优选的至少一种另外的节肢动物驱避化合物(ⅱ),所述另外的节肢动物驱避化合物(ⅱ)选自PMD(对薄荷烷-3,8-二醇)、DEET(N,N-二乙基间甲基苯甲酰胺)、IR 3535(3-丁基乙酰氨基丙酸乙酯)、KBR 3023((RS)-仲丁基-(RS)-2-(2-羟乙基)哌啶-1-羧酸酯)或邻氨基苯甲酸乙酯(2-氨基苯甲酸乙酯)。优选地,除埃卡瑞丁之外该组合物还至少包含PMD,特别优选地,该组合物包含这两种成分的组合。
除了所提及的驱避化合物(ⅰ)和(ⅱ)之外,该组合物可以包含至少一种本领域已知的对节肢动物具有驱避作用的另外的化合物,例如N-丁基-乙酰苯胺、MGK驱虫剂264、N-甲基新癸酰胺(N-Methylneodecanamide)、AI3-35765、AI3-37220(SS220)、MGK驱虫剂326、百里酚、丁香油酚、匙羹藤酚(spathulenol)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二甲酯(DMP)、碳酸二甲酯(DMC)、邻苯二甲酸二辛酯、苯甲酸苄酯、茚酮(indalone)、荆芥内酯(nepetalactone)、邻氨基苯甲酸甲酯、2-丁基-2-乙基-1,3-丙二醇、Rutgers 612、香茅油、桉树油、樟脑油、印楝油(neem oil)、柠檬草油、柠檬醛、香叶醇、香茅醇、香茅醛、胡椒酮或例如烯炔菊酯、丙氟菊酯(Profluthrin)、四氟苯菊酯、炔呋菊酯(Furamethrin)、甲氧苄氟菊酯、丙烯菊酯、丙炔菊酯(Prallethrin)、苯醚菊酯或苄氯菊酯的拟除虫菊酯,但不限于上述化合物,然而,另外的化合物不是必需的。
基于组合物的总重量,如上所述的驱避化合物(ⅰ)和(ⅱ)中的每一种在组合物中单独存在的量分别为2.5重量%至40重量%,优选5重量%至30重量%,更优选8重量%至20重量%,其中组合物中节肢动物驱避化合物(ⅰ)和(ⅱ)的总量为10重量%至80重量%,优选20重量%至60重量%,更优选25重量%至50重量%。
优选埃卡瑞丁以10-30重量%,优选15至25重量%,更优选18至22重量%的量存在于组合物中。还优选PMD存在于组合物中,特别是以5-20重量%,优选7至15重量%,更优选8-12重量%的量存在于组合物中。埃卡瑞丁可从Lanxess(德国)以商品名购得,其中PMD可以为从Citrefine(英国)获得的Galea浓缩物EC CP 680的50%溶液。值得一提的是,由Citrefine以/>形式提供的柠檬桉油也含有对薄荷烷-3,8-二醇,但不是水溶性形式。
根据本发明,基于组合物的总重量,驱避化合物(ⅰ)和(ⅱ)一起存在于组合物中的总量为10重量%至80重量%,优选20重量%至60重量%,更优选25重量%至50重量%。如果从以上所列驱避化合物的列表中,将(ⅰ)埃卡瑞丁和(ii)PMD组合,则优选组合物包含这两种化合物的组合量为组合物总重量的10重量%至80重量%,特别是15重量%至50重量%,优选20重量%至40重量%,更优选25重量%至35重量%。
如果组合物中同时存在埃卡瑞丁和PMD,则优选它们以3:1至1:2的重量比存在,优选以2.5:1至1:1.5的重量比存在,更优选以2.2:1至1:1.2的重量比存在,最优选以约2:1的重量比存在。
本发明组合物的另一种成分是(ⅲ)多元醇,其选自PPG-20甲基葡萄糖醚、PPG-10甲基葡萄糖醚、丙二醇(propylene glycol)(丙二醇(propandiol))、丁二醇(butyleneglycol)(丁二醇(butandiol))和戊二醇(pentylene glycol)(戊二醇(pentandiol))。优选组合物(ⅲ)至少包含PPG-20甲基葡萄糖醚。如果存在另外的(additional)多元醇(ⅲ),则优选该组合物还包含多元醇丙二醇和戊二醇中的至少一种,如需要,二者都包含。
基于组合物的总重量,每种多元醇(ⅲ)在组合物中单独存在的量分别为0.1重量%至10重量%,优选0.2重量%至8重量%,更优选0.3重量%至7重量%,最优选0.4重量%至6重量%,其中所述多元醇(ⅲ)在组合物中的总量为0.2重量-%至20重量%,优选0.4重量%至16重量%,更优选0.5重量%至12重量%。优选地,组合物优选以0.1重量%至1.5重量%,更优选0.2重量%至1重量%,甚至更优选0.25重量%至0.8重量%,甚至更优选0.3重量%至0.7重量%,以及最优选0.4重量%至0.6重量%的量至少包含PPG-20甲基葡萄糖醚,例如可从Lubrizol(美国,俄亥俄州)获得的此外,如果存在另外的多元醇(ⅲ),则优选所述组合物包含多元醇丙二醇和戊二醇中的至少一种,其中这两种多元醇分别彼此单独地优选以2重量%至10重量%,优选3重量%至8重量%,更优选4重量%至6重量%的量被加入。
在本发明的一个优选实施方案中,所述组合物包含(ⅰ)埃卡瑞丁,(ⅱ)PMD和(ⅲ)PPG-20甲基葡萄糖醚。该组合物可以进一步包含选自PPG-10甲基葡萄糖醚、丙二醇、丁二醇和戊二醇的另外的多元醇(ⅲ)。如果存在另外的多元醇(ⅲ),则组合物优选另外包含丙二醇和戊二醇中的至少一种,如需要,二者都包含。
已经发现,将多元醇(ⅲ)添加到包含驱避化合物(ⅰ)和任选地(ⅱ)的组合物中获得制剂的更好的效率,并且还使得所述驱避组分的有效期(period of effectiveness)的显著延长。尤其是,添加PPG-20甲基葡萄糖醚显著延长了包含(ⅰ)埃卡瑞丁的组合物的有效时间期限(effective time period)。包含埃卡瑞丁和PMB二者并且还至少包含PPG-20甲基葡萄糖醚和任选地丙二醇和戊二醇中的至少一种的组合物显示出远远超过预期值的效率(efficiency)的增加和有效期的延长。
为了平衡化合物的溶解度和驱避化合物渗透到皮肤中的可能性和程度,根据本发明的组合物优选包含最多30重量%含量的任何C1至C5醇。因此,组合物的总C1-5醇含量优选不多于30重量%,优选不多于25重量%,不多于20重量%,不多于15重量%,不多于10重量%,不多于8重量%或不多于5重量%(所有加入的C1-5醇的总含量)更优选不多于3重量%,甚至更优选不多于2重量%。尽管如此,优选加入一定量的甲醇、乙醇、丙醇或异丙醇、正丁醇或叔丁醇或戊醇中的至少一种C1-5醇,以增加有机化合物在水性介质(aqueousmedium)中的溶解度。因此,组合物可以包含0.02重量%至30重量%,优选至少0.1重量%,更优选至少0.5重量%的C1-5醇,甚至更优选至少1重量%的量的任何C1-5醇,特别是乙醇(任选变性的(denatured)或与异丙醇和/或丁醇混合的)或异丙醇。
此外,由于表面活性剂还增加了驱避化合物(ⅰ)和/或(ⅱ)对皮肤的渗透,因此特别优选该组合物包含少于5重量%的任何表面活性剂。在一个优选的实施方案中,组合物包含少于4重量%,优选少于3重量%,甚至更优选少于2.5重量%的任何表面活性剂,和少于2重量%,优选少于1.5重量%,更优选少于1重量%,甚至更优选少于0.5重量%的阴离子表面活性剂、两性表面活性剂或阳离子表面活性剂,其中优选其不包含选自阴离子表面活性剂、两性表面活性剂或阳离子表面活性剂的任何表面活性剂。因此,如果存在表面活性剂,优选所述表面活性剂是非离子表面活性剂。如果存在表面活性剂,则优选其为用作乳化剂的表面活性剂。
此类非离子乳化剂/表面活性剂的实例有:
·将2至30摩尔环氧乙烷和/或0至5摩尔环氧丙烷加成到直链C8-22脂肪醇、C12-22脂肪酸和烷基中含8至15个碳原子的烷基酚上的产物;
·将1至30摩尔环氧乙烷加成到甘油上的产物的12/18脂肪酸单酯和二酯;
·含6至22个碳原子的饱和与不饱和脂肪酸的甘油单酯和二酯以及脱水山梨醇单酯和二酯及它们的环氧乙烷加成产物;
·将15至60摩尔环氧乙烷/聚乙二醇加成到蓖麻油和/或氢化蓖麻油上的产物;
·多元醇酯,尤其是例如聚甘油多蓖麻酸酯(polyglycerol polyricinoleate)、聚甘油聚-12-羟基硬脂酸酯或聚甘油二聚合油异硬脂酸酯(polyglycerol dimerateisos-tearate)的聚甘油酯。这些类别(classes)中的几种化合物的混合物也是合适的;
·将2至15摩尔环氧乙烷加成到蓖麻油和/或氢化蓖麻油上的产物;
·基于直链、支链、不饱和或饱和C6/22脂肪酸、蓖麻油酸和12-羟基硬脂酸以及甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(例如山梨醇)、烷基葡糖苷(例如甲基葡糖苷、丁基葡糖苷、十二烷基葡糖苷)和聚葡糖苷(例如纤维素)的偏酯(partial esters);
·磷酸一烷基酯、磷酸二烷基酯和磷酸三烷基酯(mono-,di and trialkylphosphates)以及磷酸一聚乙二醇烷基酯、磷酸二聚乙二醇烷基酯和/或磷酸三聚乙二醇烷基酯(mono-,di-and/or tri-PEG-alkyl phosphates)及它们的盐;
·羊毛蜡醇;
·聚硅氧烷/聚烷基聚醚共聚物及相应的衍生物;
·季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合酯和/或C6_22脂肪酸、甲基葡萄糖和多元醇优选甘油或聚甘油的混合酯,
·聚亚烷基二醇以及
·碳酸甘油酯。
为了在将组合物施用于皮肤时提供令人愉悦的感觉,组合物优选不包含具有多于100个单体单元的聚合物化合物,优选不包含具有多于80个单体单元的聚合物化合物。通过避免具有多于100个单体单元的聚合化合物,皮肤上的“膜(film)”感效果显著降低。然而,如果优选为组合物提供防水性(water-resistance),则可将成膜聚合物(film-formingpolymer)包括在制剂中。成膜聚合物是本领域公知的,例如VP/二十碳烯共聚物(例如购自Ashland的Antaron V-220或购自Givaudan的Unimer U-15)、VP/十六碳烯共聚物(例如购自Givaudan的Unimer U-151)、三十烷基PVP(Triacontanyl PVP)(例如购自Givaudan的Unimer U-6)、苯乙烯/丙烯酸酯共聚物(例如购自Nouryon的Dermacryl E),但不限于此。
此外,为了尽可能少地损害皮肤的酸性保护膜,组合物的pH值优选为pH 4至pH 7的范围,优选为pH 4.5至pH 6的范围。为了调节组合物的pH,可以使用任何合适的化合物,如低分子量(low molecular)羧酸,如柠檬酸、酒石酸、琥珀酸、马来酸、乳酸或NaOH,如MEA(单乙烯胺)、TEA(三亚乙基胺)或四羟丙基乙二胺的任何胺,但不限于所述化合物。
本发明组合物的另一种合适且优选的成分是任意的聚乙二醇(PEG),其中除了上述多元醇(ⅲ)之外还添加了所述PEG。合适的PEG还具有少于80个乙氧基单体(EO单元)。优选地,所包含的PEG具有不多于30个EO单元,更优选不多于20个EO单元,甚至更优选不多于15个EO单元,并且最优选不多于10个EO单元,但优选至少3个EO单元,优选至少4个、至少5个或至少6个EO单元,例如6个、7个、8个或9个EO单元。特别优选的聚乙二醇是PEG-8,例如可为BASF提供的E 400。如果存在,可以以2.5重量%至40重量%,优选3.5重量%至30重量%,更优选5重量%至20重量%的量将所述聚乙二醇掺入组合物中。
除了上述组分之外,组合物还可以包含另外的常用成分。
本发明的组合物可以任选地包含一种或多种香料(perfumes)作为至少一种另外的成分。可以将香料添加到组合物中,以根据期望改善或调整产品的感官特性。合适的香料/芳香剂(fragrances)可以包括但不限于例如天然芳香剂,包括花朵(百合、薰衣草、玫瑰、茉莉、橙花、依兰)、茎和叶(天竺葵、广藿香、苦橙叶)、果实(茴香、芫荽、葛缕子(caraway)、杜松)、果皮(佛手柑、柠檬、橙)、根(肉豆蔻、当归、芹菜、小豆蔻、闭鞘姜属(costus)、鸢尾、省藤(calmus))、木材(松木、檀香、愈创木、雪松、降香)、药草和草(龙蒿、柠檬草、鼠尾草、百里香)、针叶和树枝(branches)(云杉、冷杉、松树、矮松)、树脂和香脂(白松香、榄香脂、安息香、没药、乳香、红没药(opoponax))的提取物。也可以使用动物原料,例如麝猫(civet)和海狸。典型的合成香料化合物是酯、醚、醛、酮、醇和烃类的产物。酯类香料化合物的实例是乙酸苄酯、异丁酸苯氧乙酯、乙酸对叔丁基环己酯(p-tert.butylcyclohexylacetate)、乙酸芳樟酯、乙酸二甲基苄基原酯(dimethyl benzyl carbinylacetate)、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、乙基甲基苯基甘氨酸酯、环己基丙酸烯丙酯(allyl cyclohexyl propionate)、丙酸苏合香酯(styrallyl propionate)和水杨酸苄酯。醚包括例如苄基乙醚,而醛包括例如含有8至18个碳原子的直链烷醛(alkanal)、柠檬醛、香茅醛、香茅基含氧乙醛(citronellylaxyacetaldehyd)、仙客来醛、羟基香茅醛、铃兰醛和对叔丁基苯丙醛(bourgeonal)。合适的酮的实例是紫罗兰酮、α-异甲基紫罗兰酮和甲基柏木酮。合适的醇是茴香脑、香茅醇、丁香油酚、异丁子香酚、香叶醇、芳樟醇、苯乙醇和萜品醇。烃类主要包括萜烯和香脂。然而,优选使用不同香料化合物的混合物,它们一起产生令人愉悦的香味。其他合适的芳香油(perfume oils)是挥发性相对较低的精油,它们主要用作芳香成分。实例是鼠尾草油、甘菊油、丁香油、蜂花粉油、薄荷油、肉桂叶油、酸橙花油、杜松子油、香根草油、乳香油(olibanum oil)、香叶油(galbanum oil)、金莲花油(labolanum oil)和薰衣草油(lavendin oil)。下列物质优选单独使用或以混合物的形式使用:佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛(lyral)、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄基丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(Boisambrene Forte)、降龙涎香醚(Ambroxan)、吲哚、二氢茉莉酮酸甲酯(hedione)、sandelice、柠檬油(citrus oil)、橘皮油(mandarin oil)、橙油、戊基乙醇酸烯丙酯(allylamyl glycolate)、环草酮、薰衣草油、快乐鼠尾草精油(clary oil)、β-大马酮(beta-damascone)、波旁香叶油(geranium oilbourbon)、水杨酸环己酯、甲基柏木酮(Vertofix Coeur)、龙涎酮(Iso-E-Super)、FixolideNP、橡苔(evernyl)、γ-甲基紫罗兰酮(iraldein gamma)、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚(rose oxide)、romillat、依罗酯(irotyl)和2-叔丁基环己基乙基碳酸酯(floramat)。此外,可以使用提供除臭效果的香料。
本发明的组合物可以以液体、乳霜(cream)、乳液(lotion)或凝胶(gel)的形式提供,然而优选以液体组合物的形式提供,特别是以含水组合物(aqueous composition)、W/O乳液(emulsion)或O/W乳液的形式提供。优选的是含水液体组合物。组合物可以包含基于组合物的总重量的至少5重量%至65重量%,优选至少8重量%至60重量%,更优选至少10重量%至55重量%的水。
所述组合物优选具有在20℃下的0至200帕·秒,优选在20℃下的0.5至100帕·秒,更优选在20℃下的0.8至50帕·秒的(动力学)粘度,这是根据DIN EN ISO 2555:2018使用带有L2型转子的Brookfield粘度计DV-II在20℃下以100rpm的转速测得的。
如果组合物以乳霜或乳液的形式提供,则优选它包含任何合适的油或脂肪化合物,例如基于具有6至18个,优选8至10个碳原子的脂肪醇的格尔伯特醇(Guerbetalcohols),直链C6-C22-脂肪酸与直链或支链C6-C22-脂肪醇的酯或支链C6-C13-羧酸与直链或支链C6-C22-脂肪醇的酯,例如肉豆蔻酸肉豆蔻酯、棕榈酸肉豆蔻酯、硬脂酸肉豆蔻酯、异硬脂酸肉豆蔻酯、油酸肉豆蔻酯、山嵛酸肉豆蔻酯、芥酸肉豆蔻酯(myristyl erucate)、肉豆蔻酸鲸蜡酯(cetyl myristate)、棕榈酸鲸蜡酯、硬脂酸鲸蜡酯、异硬脂酸鲸蜡酯,油酸鲸蜡酯,山嵛酸鲸蜡酯、芥酸鲸蜡酯、肉豆蔻酸硬脂醇酯(stearyl myristate)、棕榈酸硬脂醇酯、硬脂酸硬脂醇酯、异硬脂酸硬脂醇酯、油酸硬脂醇酯、山嵛酸硬脂醇酯、芥酸硬脂醇酯、肉豆蔻酸异硬脂醇酯、棕榈酸异硬脂醇酯、硬脂酸异硬脂醇酯、异硬脂酸异硬脂醇酯、油酸异硬脂醇酯、山嵛酸异硬脂醇酯、油酸异硬脂醇酯、肉豆蔻酸油酯、棕榈酸油酯、硬脂酸油酯、异硬脂酸油酯、油酸油酯、山嵛酸油酯、芥酸油酯、肉豆蔻酸山嵛酯、棕榈酸山嵛酯、硬脂酸山嵛酯、异硬脂酸山嵛酯、油酸山嵛酯、山嵛酸山嵛酯、芥酸山嵛酯、肉豆蔻酸芥酯(erucyl myristate)、棕榈酸芥酯、硬脂酸芥酯、异硬脂酸芥酯、油酸芥酯、山嵛酸芥酯和芥酸芥酯(erucyl erucate)。还合适的是直链C6-C22-脂肪酸与支链醇,特别是2-乙基己醇的酯,C18-C38-烷基羟基羧酸与直链或支链C6-C22-脂肪醇的酯,尤其是苹果酸二辛酯,直链和/或支链脂肪酸与多元醇(例如,丙二醇、二聚二醇或三聚三醇)和/或支链醇的酯、基于C6-C10-脂肪酸的甘油三酯、基于C6-C18-脂肪酸的液体甘油单/二/三酯混合物、C6-C22-脂肪醇和/或支链醇与芳族羧酸特别是苯甲酸的酯、C2-C12-二元羧酸与具有1-22个碳原子的直链或支链醇或具有2至10个碳原子和2至6个羟基的多元醇的酯、植物油、支链伯醇、取代环己烷、直链和支链C6-C22-脂肪醇碳酸酯,例如碳酸二辛酯(CC)、基于具有6至18个,优选8至10个碳原子的格尔伯特醇碳酸酯(Guerbet carbonate)、苯甲酸与直链和/或支链C6-C22醇的酯(例如/>TN)、每个烷基具有6至22个碳原子的直链或支链、对称或不对称二烷基醚、例如二辛基醚(/>OE)、环氧化脂肪酸酯与多元醇的开环产物、硅油类(环甲硅油、硅甲硅油等级(silicone methicone grades)等)、脂肪族烃或环烷烃,例如角鲨烷、角鲨烯或二烷基环己烷,和/或矿物油。
本发明的驱虫剂组合物优选具有可喷洒的低粘度,因此,它可以在配备有喷雾装置(spraying device)的容器中提供。所述喷雾装置可以是泵喷雾装置或者可以是气溶胶喷雾装置,这两种类型的装置都允许以小液滴的形式喷洒所述驱虫剂组合物。其中“小液滴”是指组合物以液滴尺寸在5nm至500μm、优选50nm至200μm、更优选100nm至100μm、甚至更优选500nm至50μm和最优选1至50μm的范围内的液滴的形式提供。
因此,优选在泵喷雾容器或气溶胶罐中提供本发明的驱虫剂组合物。如果使用气溶胶罐,则所述罐或所述组合物有利地进一步包含合适的气体推进剂,例如丙烷和/或丁烷。
本发明的驱虫剂组合物适用于驱除接触人或动物皮肤的昆虫和/或蜱,并因此驱除它们使其不叮咬所述人或动物。由于其特定的组分组合,与目前市场上提供的组合物相比,本发明的驱虫剂组合物提供了针对节肢动物物种的长效的保护。因此,与市场上已知的组合物相比,可以以更少的量使用和/或较不频繁地施用本文所述的驱虫剂组合物。由于长达(up to)12小时的有效保护,本发明的驱虫剂组合物可以例如早上施用一次,并且晚上施用一次,例如睡前施用。优选例如通过喷洒,施用组合物而使其均匀地分布在未被覆盖的人或动物皮肤上而获得保护。
具体实施方式
实施例
以下实施例示出了与未落入本发明的范围的组合物(V)相比,根据本发明的组合物(E)在驱除埃及伊蚊(Aedes aegypti)叮咬人类志愿者方面的效果。
按照标准方案,在27.5±0.5℃的温度、65-85%的相对湿度和12:12小时的光照周期(photo period)下饲养伊蚊属雌蚊。光照时间(450勒克斯(Lux))设定为8:00至20:00。从卵中孵化后,将幼虫保存在盛有1:1的脱氧自来水和去离子水的混合物的水盆(30×30×10cm)中,并投喂鱼食片(Tetra )。羽化前,将蛹转移至笼舍(40×30×20cm)内。向成年蚊提供糖溶液(10%葡萄糖(dextrose)),并在5至15日龄时用于拒虫剂试验。
将每30只蚊放入体积为27,000cm3(41×41×16cm)的测试笼中。笼舍试验在无窗户的气候室(4.5×4.5×2.5m)内进行,温度为27.5±0.5℃,并且相对湿度为65±5%rF。光强为450勒克斯。
对于实施例,制备了除了水和以下指定的成分之外,还包含合适量的PEG-8(10-25重量%)和一定量的乙醇的含水组合物。
将一定量的下表1中限定的相应组合物施用于志愿者前臂上的限定区域(definedarea)(以三重试验(triple test)进行,n=3)。施用前,用无香料肥皂清洗皮肤,用水冲洗,并用50%异丙醇擦拭。标记了一个大于测试窗口的区域,以确保暴露的皮肤完全用拒虫剂处理。标记区域的大小为约100cm2。
将试验制剂施用于每名志愿者一个前臂上的限定区域。在每个单独的疗效试验之前进行零对照试验(Zero control test),并记录直至发生10次着落(landing)的确切时间。利用该时间值,可以根据以下公式计算出对被处理手臂的驱虫保护:
在产品施用后不久首次验证了驱避效果,然后以规则的30分钟间隔再次验证,最长可达8小时(实施例V2 12小时),或直至驱避失败。每单次试验持续2分钟,在此期间记录了经处理的皮肤上的着落和叮咬次数。
使用1.首次叮咬的时间,2.与未经处理的皮肤(同一时间范围内的几次叮咬)相比,直到保护免受叮咬达到少于95%的时间来评价驱虫效果。
<95%的值表示完全保护时间的结束,并被用作驱避试验的中断(break-off)标准。
对3名志愿者进行了测试。所有志愿者都对试验蚊种有吸引力,因此符合参加驱蚊功效研究的要求。每个志愿者都有自己的笼舍。在单次试验(零对照和功效试验)之间,将笼舍连接到空气通风系统,以避免宿主气味和活性成分在笼舍内积聚。以新个体替换在测试期间开始吸血的测试蚊,以确保在整个测试日内寻找宿主的雌性数量保持不变。
表1
(1)对薄荷-3,8-二醇
(2)1-(1-甲基丙氧羰基)-2-(2-羟乙基)哌啶
(3)PPG-20甲基葡萄糖醚
(4)如果8小时内不叮咬,在12小时时取下一个值
(5)实验在12小时后停止
从实施例中可以看出,将PPG-20甲基葡萄糖醚添加到驱虫剂埃卡瑞丁中,显著增加了保护皮肤免受首次昆虫叮咬的时间段(参见V6对比E1),事实上,添加物延长了直至首次叮咬的时间,使直至首次叮咬的时间与采用两倍的量的埃卡瑞丁相比变得更长(E1对比V7)。然而,在向驱虫剂PMD中添加PPG-20甲基葡萄糖醚时,只能观察到轻微影响(参见V1对比V3和V2对比V4)。即使将相当高含量的PMD和PPG-20甲基葡萄糖醚合并(V5对比V4),也无法获得令人信服的效果。
如果将PPG-20甲基葡萄糖醚添加到包含埃卡瑞丁和PMD的组合的组合物中,则与所有其他组合物相比,直到昆虫首次叮咬的时间段和直到驱虫剂保护降至小于95%的时间段都可以显著延长(参见E2)。这种效果是不可预见的,因为在E2中两种驱虫剂同时存在于皮肤上,因此,预期对于这两种驱虫剂的组合,应获得与埃卡瑞丁单独提供的时间(其明显超过PMD的有效时间)相当的有效时间。因此,埃卡瑞丁、PMD和PPG-20甲基葡萄糖醚三种成分的组合产生了与单一驱虫剂相比,具有更好的效果的驱虫剂。
Claims (37)
1.一种节肢动物驱避组合物,其包含
埃卡瑞丁,其为1-(1-甲基丙氧羰基)-2-(2-羟乙基)哌啶且基于所述组合物的总重量在所述组合物中以8重量%至20重量%的量存在;
PMD,其为对薄荷烷-3,8-二醇且基于所述组合物的总重量在所述组合物中以8重量%至20重量%的量存在;以及
PPG-20甲基葡萄糖醚,基于所述组合物的总重量其在所述组合物中以0.1重量%至1.5重量%的量存在。
2.根据权利要求1所述的节肢动物驱避组合物,其还包含选自PPG-10甲基葡萄糖醚、丙二醇、丁二醇、戊二醇中的至少一种另外的多元醇。
3.根据权利要求2所述的节肢动物驱避组合物,所述至少一种另外的多元醇选自丙二醇和戊二醇。
4.根据权利要求1所述的节肢动物驱避组合物,其中基于所述组合物的总重量,节肢动物驱避化合物在所述组合物中的总量为10重量%至80重量%。
5.根据权利要求4所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述节肢动物驱避化合物在所述组合物中的总量为20重量%至60重量%。
6.根据权利要求5所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述节肢动物驱避化合物在所述组合物中的总量为25重量%至50重量%。
7.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.1重量%至10重量%。
8.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.1重量%至10重量%。
9.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.2重量%至8重量%。
10.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.2重量%至8重量%。
11.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.3重量%至7重量%。
12.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.3重量%至7重量%。
13.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.4重量%至6重量%。
14.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述至少一种另外的多元醇中的每一种在所述组合物中单独存在的量为0.4重量%至6重量%。
15.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述多元醇在所述组合物中的总量为0.2重量%至20重量%。
16.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述多元醇在所述组合物中的总量为0.4重量%至16重量%。
17.根据权利要求2所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述多元醇在所述组合物中的总量为0.5重量%至12重量%。
18.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述多元醇在所述组合物中的总量为0.2重量%至20重量%。
19.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述多元醇在所述组合物中的总量为0.4重量%至16重量%。
20.根据权利要求3所述的节肢动物驱避组合物,其中基于所述组合物的总重量,所述多元醇在所述组合物中的总量为0.5重量%至12重量%。
21.根据权利要求1所述的节肢动物驱避组合物,其包含重量比为3:1至1:2的埃卡瑞丁和PMD。
22.根据权利要求21所述的节肢动物驱避组合物,其包含重量比为2.5:1至1:1.5的埃卡瑞丁和PMD。
23.根据权利要求22所述的节肢动物驱避组合物,其包含重量比为2.2:1至1:1.2的埃卡瑞丁和PMD。
24.根据权利要求23所述的节肢动物驱避组合物,其包含重量比2:1的埃卡瑞丁和PMD。
25.根据权利要求1所述的节肢动物驱避组合物,其包含基于所述组合物的总重量的0.2重量%至1重量%的PPG-20甲基葡萄糖醚。
26.根据权利要求25所述的节肢动物驱避组合物,其包含基于所述组合物的总重量的0.25重量%至0.8重量%的PPG-20甲基葡萄糖醚。
27.根据权利要求26所述的节肢动物驱避组合物,其包含基于所述组合物的总重量的0.3重量%至0.7重量%的PPG-20甲基葡萄糖醚。
28.根据权利要求27所述的节肢动物驱避组合物,其包含基于所述组合物的总重量的0.4重量%至0.6重量%的PPG-20甲基葡萄糖醚。
29.根据权利要求1所述的节肢动物驱避组合物,其包含
(ⅰ)不多于30重量%的任何C1-5醇和/或
(ⅱ)不包含具有多于100个单体单元的聚合物化合物,和/或
(ⅲ)少于5重量%的任何表面活性剂。
30.根据权利要求1所述的节肢动物驱避组合物,其满足以下至少一项:
(ⅰ)所述组合物是液体、乳霜、乳液或凝胶,
(ⅱ)所述组合物包含基于所述组合物的总重量的至少5重量%至65重量%的水,
(ⅲ)所述组合物在20℃下的粘度为0至200帕·秒。
31.根据权利要求1所述的节肢动物驱避组合物,除PPG-20甲基葡萄糖醚外,其还包含具有最大80个EO单元的聚乙二醇。
32.根据权利要求2所述的节肢动物驱避组合物,除所述至少一种另外的多元醇外,其还包含具有最大80个EO单元的聚乙二醇。
33.根据权利要求1所述的节肢动物驱避组合物,其pH值在pH 4至pH7的范围内。
34.根据权利要求33所述的节肢动物驱避组合物,其pH值在pH 4.5至pH 6的范围内。
35.根据权利要求1所述的节肢动物驱避组合物,其被提供在具有允许以微滴形式喷洒所述组合物的喷雾装置的容器中。
36.根据权利要求1至35任一项所述的节肢动物驱避组合物在用于驱避昆虫和/或蜱接触人或动物的皮肤和/或驱避昆虫和/或蜱叮咬中的用途。
37.用于驱避昆虫或蜱接触人或动物的皮肤和/或驱避昆虫或蜱叮咬的方法,其包括将权利要求1至35中任一项所述的节肢动物驱避组合物施用于所述人或动物的皮肤。
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EP3763212A1 (en) | 2021-01-13 |
ES2899666T3 (es) | 2022-03-14 |
JP2022540844A (ja) | 2022-09-20 |
HRP20211781T1 (hr) | 2022-02-18 |
TW202116166A (zh) | 2021-05-01 |
AU2020309776A1 (en) | 2021-12-23 |
US11503831B2 (en) | 2022-11-22 |
JP7482210B2 (ja) | 2024-05-13 |
AR119371A1 (es) | 2021-12-15 |
CA3144822A1 (en) | 2021-01-14 |
KR20220032013A (ko) | 2022-03-15 |
US20210007354A1 (en) | 2021-01-14 |
PT3763212T (pt) | 2021-11-22 |
MX2022000370A (es) | 2022-04-25 |
LT3763212T (lt) | 2021-12-27 |
RS62661B1 (sr) | 2021-12-31 |
HUE057039T2 (hu) | 2022-04-28 |
BR112022000051A2 (pt) | 2022-02-22 |
EP3763212B1 (en) | 2021-08-18 |
SI3763212T1 (sl) | 2022-01-31 |
WO2021005206A1 (en) | 2021-01-14 |
CN114206111A (zh) | 2022-03-18 |
PL3763212T3 (pl) | 2022-01-17 |
DK3763212T3 (da) | 2021-11-15 |
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