CN1251988A - 包含生物活性成分的粘合微胶囊 - Google Patents

包含生物活性成分的粘合微胶囊 Download PDF

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CN1251988A
CN1251988A CN98804015A CN98804015A CN1251988A CN 1251988 A CN1251988 A CN 1251988A CN 98804015 A CN98804015 A CN 98804015A CN 98804015 A CN98804015 A CN 98804015A CN 1251988 A CN1251988 A CN 1251988A
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A·森古普塔
K·E·尼尔森
G·巴林施泰因
K·李
J·巴诺维茨
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, 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 in coated particulate form
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Abstract

一种包含生物活性物质的微胶囊的水性悬浮液包含其量能有效地使所述微胶囊粘合到所需基底上的粘合剂材料。

Description

包含生物活性成分的粘合微胶囊
发明的领域
本发明涉及包含生物活性成分的粘合胶囊的悬浮体。
发明的背景
已知常通过界面缩聚用胶囊包封各种物质。例如,美国专利3,577,515提及一些胶囊,它们包含染料、油墨、化学试剂、药物、香料、杀虫剂、除草剂、过氧化物和实际上可以溶解、悬浮或以其它方式包括在内或作为液体包在胶囊中的任何物质。英国专利1,371,179披露了制备聚脲胶囊的方法,所述胶囊包含染料、油墨、化学试剂、药物、香料、杀真菌剂、杀菌剂和农药如除草剂和杀虫剂。美国专利4,046,741;4,140,516;4,417,916;4,563,212和欧洲专利611,253涉及各种物质的胶囊化。加拿大专利1,044,134涉及杀虫剂,尤其是拟除虫菊酯的胶囊化。加拿大专利1,179,682涉及信息素的胶囊化。与该申请同一天申请的未审定美国专利申请(代理人登记号53319USA6A)也涉及用胶囊包封各种物质,包括生物活性物质如信息素。
上述专利利用各种形式的界面缩聚,尤其是形成含有聚脲和/或聚氨酯/聚脲壳壁的胶囊。据称用各种方法制成的胶囊的直径在约1微米至约2毫米的范围内,但大多数落在该范围的较低一端,即约250微米,或甚至为100微米,低至约1微米。
本发明的概述
微胶囊的水性悬浮液包含生物活性物质,该悬浮液还包含其量能有效地使所述微胶囊粘合到所需基底(substrate)上的粘合剂材料。
较好实例的描述
为本发明的目的,术语“生物活性的”是指影响有机体生命过程的物质。生物活性的物质包括除草剂、杀虫剂、药物和化学信息素,包括天然和人工合成的信息素。
包含这些生物活性成分并且另外还包含粘合剂材料的微胶囊宜通过喷雾来施加。这在林业、农业和园艺业领域中是特别有利的,其中空中喷洒是一种较好的施加方式。将喷雾过的胶囊施加到叶片上,在叶片上希望进行持续的接触。例如,杀虫剂和信息素应保留在假定它们可能显示出最大效果的叶片上。在不存在本文所述的粘合剂材料的情况下,该微胶囊会被风和雨吹掉或冲刷掉。必需的是,使胶囊有粘性的任何处理都不应以牺牲其它有价值的性能为代价。例如,对于林业、农业或园艺业所用的喷雾,胶囊理想上是分散的颗粒,通常用悬浮剂将其保持在水悬浮液中。粘性不应使胶囊具有这样的结果,即胶囊在水性悬浮液中聚集在一起。这种聚集当然会使胶囊不适于喷雾,并且破坏胶囊的全部用途。而且,用来赋予粘性的任何材料应不会影响颗粒的完整性;它应不会溶解或弄薄胶囊的壳。
本发明的组合物是水性悬浮液,它在使用中提供明显的优点。其它释放包囊的杀虫剂和除草剂的组合物是溶剂型的,它有明显的缺点,因为这种溶液将挥发性有机化合物(VOC)释放到环境中。为本发明的目的,挥发性有机化合物(VOC)是在20℃时蒸汽压大于0.1托(mm Hg)的任何挥发性有机物质,它不是活性成分(例如杀虫剂、除草剂等)。更可取的是,可以将挥发性有机化合物定义为在20℃时蒸汽压大于0.02托、不是活性成分的物质。由于本发明的水性悬浮液不需要包含任何可观量的这些不希望有的VOC,所以整个组合物对环境明显是更有利的。本发明较好的组合物包含不大于5重量%的VOC,最好包含不大于2重量%的VOC。有显著空气污染问题的诸如洛杉矶等管辖区域将会发现本发明的水性悬浮液是非常好的,原因是其对环境的污染影响小。
尽管粘合剂材料目前有时用在农业中以帮助除草剂和杀虫剂粘附到有机基底上,但迄今为止仅对未包囊的化学品在有限范围内使用胶乳。令人惊奇地发现对微胶囊包封的生物活性物质加入粘合剂会获得一种仍可从常规喷雾设备中喷雾的组合物。与预料的相反,业已发现本发明组合物的粘性微胶囊在喷雾孔或贮藏容器中不会聚集。在施加过程中,粘合剂胶乳与微胶囊结合,所以它不会完全涂覆目标基底的表面。由于粘合剂溶解在或分散在水中,所以在风吹雨打最终将该材料从基底上除去之前,该组合物在目标基底上有有限但有效的使用寿命。
本发明组合物中所用的粘合剂胶乳可以是已有技术中有用的任何合适的水分散性粘合剂。在农业上,这种胶乳组合物通常称为粘着剂或展涂剂(spreaders)。粘着剂用于帮助未包囊的农业化学品粘合到植物上。展涂剂用于在施加时帮助分散未包囊的农业化学品。较好的粘合剂是丙烯酸酯基粘合剂。一种合适的胶乳以商标Companion购自Rohm & Haas。另一种是以商标DPI S-100购自DeerpointIndustries(一种专有的粘着剂/展涂剂)。这种粘合剂的例子是由诸如丙烯酸正丁酯、丙烯酸异辛酯等“软”单体制成的聚合物,或由诸如异丁烯、丙烯酸正丁酯、丙烯酸异辛酯、丙烯酸乙基己酯等软组分和诸如丙烯酸、丙烯腈、丙烯酰胺、甲基丙烯酸、甲基丙烯酸甲酯等极性单体制成的共聚物。非球形聚丙烯酸酯粘合剂是市售的,例如以Rohm and Haas RhoplexTM系列的粘合剂。非球形聚丙烯酸酯粘合剂在整个悬浮液中所占的量较好约为10-35重量%。
进一步令人惊奇地发现粘合剂的粘性微球体可用于将含生物活性物质的微胶囊粘合到所需的基底上。粘性微球体具有足够的粘合性以提供所需的粘合功能,并且对完全涂覆微胶囊和可能抑制胶囊的释放性能没有损害。令人惊奇的是,可以在不需要改进常规喷雾器孔并且堵塞问题是最小的情况下,施加含生物活性物质的微胶囊和粘性微球体的混合物。
粘合剂材料较好是丙烯酸酯或甲基丙烯酸酯基粘合剂体系,它包含如美国专利3,691,140中所披露的不熔的、溶剂分散的、溶剂不溶的、固有粘性的弹性共聚物微球体。或者,该粘合剂组合物可以包含如美国专利5,045,569中所披露的中空的、聚合物、丙烯酸酯、不熔的、固有粘性的、溶剂不溶的、溶剂分散的弹性压敏粘合剂微球体。其它合适的粘合剂是如美国专利5,508,313中所披露的含有侧链亲水聚合物和低聚物部分的粘性微球体。
或者,粘合剂包含约60-100重量%直径至少为1微米的中空的、聚合的、丙烯酸酯、固有粘性的、不熔的、溶剂不溶的、溶剂分散的弹性压敏粘合剂微球体,和约0-40重量%非球形的聚丙烯酸酯粘合剂。中空微球体按欧洲专利申请371,635中所述的方法来制备。
生物活性物质较好地选自药物、杀真菌剂、杀菌剂和农药如除草剂和杀虫剂。特别好的生物活性物质是拟除虫菊酯、信息素和其它这种化学信息素,不管其是天然制得的或是人工合成的。
微胶囊可以是任何适用于用胶囊包封生物活性物质的微胶囊,它包括聚脲、聚氨酯、蜜胺/脲、明胶微胶囊等。包含生物活性物质的微胶囊的大小较好为1微米至2毫米。
本发明也提供一种制备粘合微胶囊的水性悬浮液的方法。业已令人惊奇地发现在碱性条件下小心地混合本发明组合物的各成分对避免形成凝块是特别有利的,所述凝块会导致不可能使用常规喷雾设备来施加。该方法包括将A)pH值大于或小于7的微胶囊的水性悬浮液与B)pH值大于或小于7的粘合剂的水性悬浮液相混和,使A)和B)的pH值都大于7或都小于7。粘合剂悬浮液选自粘合的微球体、非球形水性胶乳粘合剂或粘合的微球体和非球形水性胶乳粘合剂的混合物。更好的是,混合在pH值约为8至9的条件下进行。任何碱都可用于控制pH值,例如碱金属或碱土金属氢氧化物或碳酸盐,但最简单和较好的是氨水溶液。
一般来说,本发明微胶囊的水性悬浮液A)在与粘合剂组合物混合前可以包含约5-40重量%的微胶囊,较好约5-25重量%的微胶囊。一般来说,粘合剂的水性悬浮液B)在与微胶囊组合物混合前可以包含约5-60重量%的粘合剂,较好约25-40重量%的粘合剂。合适地是将约10-30重量份粘合剂微球体的水性悬浮液(组合物B)加到约90-70重量份微胶囊的水性悬浮液(组合物A)中,形成本发明的悬浮液。若使用非球形粘合剂材料的胶乳,则其量再次合适地为约10-30重量份,将其加到约90-70重量份的微胶囊悬浮液中。
微胶囊的水性悬浮液和粘合剂微球体的水性悬浮液或含粘合剂材料的胶乳应在搅拌下缓慢和小心地混合,以避免破坏悬浮液。混合适合在室温下进行。
如上所述,本发明的组合物特别适于以容易和经济的方式传送到所需的基底上。具体地说,本发明的组合物能容易和有效地传送到有机基底如叶片、作物和杂草上。独特的配方能将包含生物活性成分的微胶囊粘合到这些有机物质上,不会过度涂覆基底并且不会无意干扰其生命过程。类似地,可以容易地将本发明的组合物施加到非人体的皮肤和毛发上以及人体需要治疗的部位上。而且,可以以有效的方式在将活性成分很好地保留在所需基底上的情况下,将本发明的组合物施加到非有机基底,如建筑物、人行道、地面等上。
业已令人惊奇地发现微胶囊和粘合剂材料的水性悬浮液可以通过喷雾装置以气溶胶的形式经济地施加到所需基底上。这种施加方法宜用于含任何填充材料的微胶囊,但特别适用于包含生物活性物质的微胶囊。在这种情况下,所需的基底较好是叶片、作物或杂草。粘合剂材料最好是粘合剂微球体的水性悬浮液。这种微球体令人惊奇地具有对所需基底的优良粘合性,并且不会涂覆微胶囊或抑制其包囊内物质的释放。
美国专利3,691,140;5,045,569和5,508,313和欧洲专利申请371,365以及上述专利申请(代理人登记号53319 USA 6A)所披露的内容在此参考引用。
用下述实施例举例说明本发明。
实施例1
用NH4OH(8g,在20g水中)中和粘合剂微球体(20g,如美国专利5,508,313中实施例2所述,其IOA∶AA∶Carbowax之比为97∶2∶1)的水性悬浮液。在搅拌下加入包囊在聚脲壳(50 g)中的信息素,E-11-十四烯-1-基乙酸酯,和rhamsam胶悬浮剂的微胶囊水性悬浮液。获得粘合微胶囊的良好悬浮液。
在对比试验中,将粘合剂微球体(20g,如上所述)与20g水混合。在搅拌下加入在聚脲壳(50g)中的E-11-十四烯-1-基乙酸酯,和rhamsun胶悬浮剂的微胶囊水性悬浮液。各组分凝结起来,尽管进一步用80g水进行稀释,但仍获得了无用的凝块。

Claims (23)

1.一种包含生物活性物质的微胶囊的水性悬浮液,该悬浮液还包含其量能有效地使所述微胶囊粘合到所需基底上的粘合剂材料。
2.如权利要求1所述的悬浮液,其中粘合剂材料的形式是粘合剂微球体的水性悬浮液。
3.如权利要求1所述的悬浮液,其中粘合剂材料的形式是非球形粘合剂胶乳。
4.如权利要求2所述的悬浮液,其中粘合剂微球体是丙烯酸酯或甲基丙烯酸酯基的、不熔的、溶剂分散的、溶剂不溶的、固有粘性的弹性共聚物微球体。
5.如权利要求1所述的悬浮液,其中粘合剂微球体是中空的。
6.如权利要求1所述的悬浮液,其中悬浮液的粘合剂组分包含约60-100重量%直径至少为1微米的中空的、聚合的、丙烯酸酯、固有粘性的、不熔的、溶剂不溶的、溶剂分散的弹性压敏粘合剂微球体,和约0-40重量%非球形的聚丙烯酸酯粘合剂。
7.如权利要求1所述的悬浮液,其中生物活性物质是药物。
8.如权利要求1所述的悬浮液,其中生物活性物质选自杀真菌剂和杀菌剂。
9.如权利要求1所述的悬浮液,其中生物活性物质是农药。
10.如权利要求8所述的悬浮液,其中生物活性物质选自除草剂和杀虫剂。
11.如权利要求1所述的悬浮液,其中生物活性物质选自拟除虫菊酯和信息素。
12.如权利要求1所述的悬浮液,其中微胶囊由在壳中包囊的生物活性物质组成,所述壳选自聚脲、聚氨酯、蜜胺/脲和明胶。
13.如权利要求1所述的悬浮液,其中微胶囊的大小为1微米至2毫米。
14.一种制备粘合微胶囊的水性悬浮液的方法,该方法包括将pH值约大于7的微胶囊的水性悬浮液A)与pH值约大于7的粘合剂的水性悬浮液B)相混和,所述粘合剂选自粘合的微球体、非球形水性胶乳粘合剂或粘合的微球体和非球形水性胶乳粘合剂的混合物。
15.如权利要求14所述的方法,其中使用氨水,使pH值约大于7。
16.如权利要求14所述的方法,其中pH值约为8至9。
17.一种制备粘合微胶囊的水性悬浮液的方法,该方法包括将pH值约小于7的微胶囊的水性悬浮液A)与pH值约小于7的粘合剂的水性悬浮液B)相混和,所述粘合剂选自粘合的微球体、非球形水性胶乳粘合剂或粘合的微球体和非球形水性胶乳粘合剂的混合物。
18.如权利要求14所述的方法,其中粘合剂的水性悬浮液B)在与微胶囊组合物A)混合前包含约5-60重量%的粘合剂。
19.如权利要求14所述的方法,其中粘合剂微球体的水性悬浮液B)在与微胶囊组合物A)混合前包含约25-40重量%的粘合剂。
20.如权利要求14所述的方法,其中将约10-30重量份粘合剂微球体的水性悬浮液(组合物B)加到约90-70重量份微胶囊的水性悬浮液(组合物A)中。
21.一种将微胶囊施加到所需基底上的方法,它包括:
a)制备微胶囊的水性悬浮液,该悬浮液还包含其量能有效地使所述微胶囊粘合到所需基底上的粘合剂材料,
b)通过喷雾装置以气溶胶的形式将所述悬浮液传送到所需基底上。
22.如权利要求20所述的方法,其中所需基底选自叶片、作物和杂草。
23.如权利要求20所述的方法,其中粘合剂材料是粘合剂微球体的水性悬浮液。
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