CN1045682A - 杀生剂的和农药的悬浮剂 - Google Patents
杀生剂的和农药的悬浮剂 Download PDFInfo
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- CN1045682A CN1045682A CN90102296A CN90102296A CN1045682A CN 1045682 A CN1045682 A CN 1045682A CN 90102296 A CN90102296 A CN 90102296A CN 90102296 A CN90102296 A CN 90102296A CN 1045682 A CN1045682 A CN 1045682A
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- Prior art keywords
- surfactant
- water
- aforesaid
- suspending agent
- agricultural chemicals
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Classifications
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- 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
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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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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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
- A01N25/02—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
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
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- Environmental Sciences (AREA)
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- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract
一种包含水溶性结构表面活性剂的悬浮剂,其中悬浮一种基本上不溶于水的或微溶于水的杀生剂或农药的颗粒或液滴,整个悬浮剂中表面活性剂与所述有效物质按重量比小于20∶1。
Description
本发明提供一种有关不溶于水的杀生剂或农药的有效药剂悬浮在水介质中的新方法,这个方法不需要使用对环境有害的溶剂。“农药”在此广义地概括了那些杀死,诱捕,驱赶或抑制有害生物体(害虫)生长或繁殖;或保护或促进所需生物,如粮食作物,观赏植物,家畜的健康生长或繁殖的化学品。这种悬浮剂用于农业,园艺,林业,畜牧业,水处理和土地管理,例如应用于田间、作物、果园、家畜、花园,林场、树篱、公园、工业领地、工地、机场、公路、铁路、河流、湖泊、池塘、沟渠、灌溉和排水工程等等。
害虫包括脊椎动物类的害虫、如啮齿类,野兔和鸽子,非脊椎动物类的害虫,如昆虫,螨,蛞蝓、蜗牛、线虫、扁虫、千足虫和致病的原生动物、杂草、真菌、霉菌、苔藓、地衣、藻类、酵母、细菌和病毒。
“杀虫剂的和农药的有效物质包括用于杀灭,诱捕,驱赶或防止或抑制前述任意一种或全部害虫的生长及繁殖的物质。它们也包括象激素、生长素、赤霉素、营养素等生长促进剂,应用于土壤或作物中的微量元素和用于水处理的杀生剂,例如锅炉水、加工水、冷却水、油田注射水、集中供暖和空调系统,但动物饲料和兽医用的内服制剂除外。
一些实质上难溶于水的杀生剂的和农药的物质广泛地用于防治有害物和/或促进作物及家畜的健康生长。为此,这些物质往往需要或采用流动态、最好是以稀释的形态使用。这就需要在一种适于用水稀释的稳定的水基质浓度里配制有效物质。
迄今为止,配制多种低水溶性农药的唯一实用方法是把农药溶于一种有机的非水混溶的溶剂中并使生成的有机溶液在水中乳化。常用的溶剂是象二甲苯或异佛尔酮的物质。从生态学和对人安全来看这种方法的一个缺点是使用溶剂没有好处。仅仅是从配制许多农药缺少实用的另外手段这一点,就已经构成了使用这类溶剂的严重限制。
应用那些低水溶性农药的其它方案包括配制成可湿性粉剂或可分散的颗粒剂,这两种方案的问题都是使用者在液体中处理固体和配制制剂。曾经试图制备农药的浓水悬剂,但是在处理或稀释时经常遇到缺乏稳定性,导致放置时沉积和/或高粘度的困难,和/或由于使用昂贵的分散剂和增稠剂带来高消耗费用的不利。我们现在已经发现了一种使有关的憎水性杀生剂和农药形成高浓缩的、稳定的、可浇注的、水基质的悬浮剂的方法,这些悬浮剂适于在使用前用水稀释,此种方法不依赖于使用有潜在危害的溶剂。这一发明可以广泛地用于把不溶的或微溶的杀生剂和农药配制成稳定的悬浮剂,包括许多迄今只能在有机溶剂中应用的、或作为可湿性粉剂、或可分散的颗粒剂、或作为不稳定的悬浮剂。
我们发现那些基本上不溶或微溶于水的杀生剂和农药可以悬浮于含水结构的表面活性剂体系中,按重量计算,它的浓度高达10-70%或更高。“结构的表面活性剂体系”。表示一种水体系,在这种体系中表面活性剂形成比一般球状胶囊更大的结构中间相,它们互相作用使得该含水介质具有摇溶性质。这种结构可以是固体、中间相或液体,也可以是多层球粒态的或在该体系中周期间断分散的或乳化的薄层,或者形成弱的网状结构或棒状或盘状结构。这种结构的大小有代表性地在0.01至200微米的范围内,最好是0.5至20微米。结构的表面活性剂体系常由表面活性剂与溶解了的电解质的盐或碱相互作用形成。这种体系目前存在于一些液体去污剂和洗涤剂的组合物中,对此在GB-2,123,846和GB-A-2,153,380中已有描述。
使用结构的表面活性剂来悬浮农药可以带来许多潜在的好处。在许多情况里,它增加了有效物质的活性和/或选择性。结构的表面活性剂能够悬浮微粒大小的范围比较广,并通过适当地选择表面活性剂而适当PH值较宽的范围,这种体系一般可以得到有利于湿磨的剪切稳定态。
我们的发明提供了一种包含水溶性结构表面活性剂的悬浮剂,其中悬浮一种基本上不溶于水或微溶于水的杀生剂或农药的颗粒或液滴。整个悬浮剂中表面活性剂与所述有效物质按重量比小于20∶1。尤其是我们的发明提供了一种悬浮剂,它包含有水、足以提供一种固体悬浮结构的表面活性剂、以及形成所述结构中足以溶解的表面活性剂减溶的电解质。
较好的产品是薄层结构,如在GB-2,123,846中描述的那样;或者最好象GB-A-2,153,380中所描述的球状结构。
我们发明的组合物中表面活性剂最好至少是含3%,常见的至少是4%,例如至少按重量计算5%。尽管我们从经济角度考虑宁愿使用较低浓度的表面活性剂,例如使用低于30%,常见的低于20%,最好低于15%,例如使用按重量计算7-10%的表面活性剂,但是在组合物中表面活性剂按重量计算可高达35%。
举例来说,表面活性剂主要可以由微溶于水的磺酸或单酯化的硫酸盐组成,例如烷基苯磺酸盐,烷基硫酸盐(酯)、烷基醚硫酸盐(酯)、烯烃磺酸盐(酯)、烷烃磺酸盐(酯)、烷基酚硫酸盐(酯)、烷基酚醚硫酸盐(酯)、烷基乙醇胺化硫酸盐(酯)、烷基乙醇胺化醚硫酸盐(酯),或α-磺基脂肪酸或其酯,每个至少含有一个烷基或烯基团,这些基团有8-22个碳原子,常见的是10-20个脂族碳原子。所说的烷基或烯基团最好是直链的伯基团,但也可以选用仲或支链的基团。这里的“醚”表示氧化烯烃和均聚和混聚的氧化烯类如聚氧化乙烯,聚氧化丙烯,甘油基和混聚氧化乙烯-氧化丙烯或混聚甘油基-氧化乙烯、甘油基-氧化丙烯基团,或甘油基-氧化乙烯-氧化丙烯基团,有代表性的含有1到20个氧化烯基团。例如磺酸盐型、硫酸盐型的表面活性剂可以是十二烷基苯磺酸钠,十六烷基苯磺酸钾,十二烷基-二甲基苯磺酸钠,月桂基硫酸钠,牛脂基硫酸钠、油基硫酸钾,月桂基单乙氧基硫酸铵,或单乙醇胺十六烷基10摩尔乙氧基化硫酸盐。
根据本发明,另外的有用阴离子表面活性剂包括脂肪烷基磺基丁二酸盐(酯),脂肪烷基醚磺基丁二酸盐(酯),脂肪烷基磺基丁酰胺酸盐(酯),脂肪烷基醚磺基丁酰胺酸盐(酯)、脂酰基肌氨酸盐(酯),脂酰基氨基乙磺酸盐(酯),羟乙磺酸盐(酯)、象硬脂酸盐(酯)、棕榈酸盐(酯)、树脂酸盐(酯)、油酸盐(酯)、亚油酸盐(酯)、松脂这样的肥皂,以及烷基醚羧酸盐(酯)和皂角甙。阴离子磷酸盐(酯)类包括象卵磷脂这样天然存在的表面活性剂也可应用。在每一种情况里,阴离子表面活性剂典型地至少含有一种8至22个碳原子,最好10到20个,通常是平均12至18个碳原子的脂肪烃链,一个象磺酸基,酸性硫酸酯、羧基、膦酸基或酸性磷酸酯基这样的可以离子化的酸性基团。在醚的情况中,它含有一个或多个甘油基和/或1到20个乙烯氧基和/或丙烯氧基团。
优选的阴离子表面活性剂是钠盐。其它有关的商品盐包括钾、锂、钙、镁、铵、单乙醇胺、二乙醇胺、三乙醇胺和至多有7个脂族碳原子的烷基胺的盐。
表面活性剂也可以是任意地含有非离子表面活性剂或由非离子型表面活性剂组成。非离子表面活性剂可以是C10-22单或二低烷基醇胺的烷基醇酰胺,就象椰子或牛脂单乙醇酰胺化物或二乙醇酰胺化物。其它可以任选的非离子表面活性剂包括乙氧基化醇,乙氧基化羧酸,乙氧基化胺,乙氧基化烷基醇酰胺化物,乙氧基化烷基酚,乙氧基化甘油酯,乙氧基化脱水山梨糖醇酯,乙氧基化磷酸盐(酯)以及丙氧基化,丁氧基化和混合乙氧/丙氧和/或丁氧类似的所有前述的乙氧基化非离子化物,所有的都具有C8-22烷基或烯基团,最多含有20个乙烯氧基和/或丙烯氧基和/或丁烯氧基团,或任意的迄今已用到粉剂或液体洗涤剂组合物中,如胺氧化物的其它非离子表面活性剂。后一种一般至少具有C8-22最好是C10-20烷基或烯基团,并且最多可以有两个低级(如C1-4、最好C1-2)烷基团。
我们发明中优选的非离子表面活性剂HLB范围是6-18,如8-12。
我们的组合物中可以包含有阳离子型表面活性剂,它包括季胺,该胺至少有一条长链(例如C12-22,典型的C16-20)烷基或烯基团和一任意的苄基,四个季胺取代基中剩余的是短链(如C1-4)烷基团。它们也包括咪唑啉和至少有一个长链烷基或烯基的季铵化咪唑啉,以及酰胺基胺和至少有一个长链烷基或烯基的季铵化酰胺基胺。季铵化表面活性剂常常是给予水溶解度测量的所有阴离子的盐,如甲酸盐(酯)、乙酸盐(酯)、乳酸盐(酯),洒石酸盐(酯),氯化物,甲基硫酸盐(酯)、乙基硫酸盐(酯),硫酸盐(酯)或硝酸盐(酯)。
我们发明的组合物也包括一种或多种两性表面活性剂,它们包括内铵盐、磺酸内铵盐和磷酸内铵盐,它们是由具有一个长链烷基或烯基的合适的三级氮化合物与适当的试剂如氯代乙酸或丙磺酸内酯反应形成的。适宜的含三级氮化合物的例子包括,有一个或两个长链烷基或烯基团,可以有一个苄基,其余的取代基是短链的烷基三级胺,有一个或二个长链烷基或烯基的咪唑啉和有一个或两个长链烷基或烯基的酰胺基胺。
上述特指的表面活性剂类型仅仅是适合于本发明应用较为普通的表面活性剂。任何能够形成结构体系的表面活性剂都可以包括在本发明内。在Schwartz Perry和Berch所著的“Surface Active Age-nts and Detergent”中,对商业上可以得到的主要表面活性剂类型做了充分的描述。
溶解的电解质化合物是我们组合物中极其重要的组分。为此,本说明书中“电解质”意思是指任何水溶性的、可以离子化的、非表面活性的化合物,它们倾向于从溶液或胶囊溶液中将表面活性剂减溶或“盐析”。尽管没有电解质存在时也可以制备结构的体系,但是除非表面活性剂是经过认真选择的,否则如果表面活性剂有足够高的浓度,这种体系的流动性常常是不够的。加入电解质可以制备含有相对比较低浓度的表面活性剂的流动性结构体系。
电解质存在的浓度最高时可以达到饱和。一般来说表面活性剂存在的越少,则需要电解质越多,以形成一种可支持固体物质的结构。我们总是愿意使用高浓度的电解质和低浓度的表面活性剂,选择经济上便宜的电解质。这样以整个组合物总重量为基准,电解质存在的浓度通常不少于1%,常见的至少是2%,例如大于3%,最好大于4%,特别是大于5%。通常浓度小于30%,更常见的小于20%,例如小于15%的重量百分比。一般浓度在5%和12%之间。
在另外的情况中,最高电解质的浓度取决于结构的类型、需要的粘度和成本。我们选取象我们在GB-A-2,153,380中所描述的球状结构那样,以求得在流动性和悬浮农药的高含量之间满意的平衡。相对于表面活性剂任何特殊类型和数量来说,最适的电解质浓度可由我们前述申请所述的方法确定。这一种方法是通过增加电解质浓度时观察电导值的变化,直到观察到第一个电导最小值。样品可以20,000G离心90分钟制备和试验,调节电解质的浓度以获得一种在离心机中不分为两相的悬浮介质。较好的电解质浓度调到提供一种在常温或在0℃或40℃下放置三个月不沉淀的组合物。较好的电解质浓度也可以被调节到提供一种切变稳定的组合物,并且希望这暴露在正常切变下基本上不增加粘度。
另外,可以加入有效的电解质以形成一种在GB-2,123,846中所述的层状体系,例如,通过加入足够的电解质保证以800G离心十七小时,分离液体悬浮介质以形成一种很小或没有表面活性剂的碱液相。可以调节配方中水量,以在流动性和稳定度之间达到一种最适宜的平衡。
除了费用之外,选择电解质取决于悬浮剂予期的作用。用于保护作物的杀真菌或杀害虫的悬浮剂最好是含非植物毒性的电解质,或它的浓度高到不足以损害作物。除草的组合物可以含有辅助的或协同的除草剂作为电解质或其相应的部分。选择的电解质也可能是与悬浮的固体在化学上共存的。本发明所用的典型电解质包括碱金属,碱土金属,铵或者胺与氯离子、溴离子、碘离子、氟离子、正磷酸、焦磷酸、膦酸、硫酸、碳酸氢根、碳酸、硼酸、硝酸、氯酸、铬酸、甲酸、乙酸、草酸、柠檬酸、乳酸、洒石酸、硅酸、高氯酸形成的盐。如果需要调节PH,例如改进悬浮固体或分散液体的稳定性或降低植物毒性,可以使用象盐酸、硫酸、磷酸或乙酸,或钠、钾、铵或钙的氢氧化物,或碱性硅酸盐这样的酸或碱。
选择植物营养剂作为或部分作为电解质是很方便的,如用硝酸盐,钾碱和/或磷酸盐。它应该避免与表面活性剂形成难溶的沉淀,或者在放置时产生大晶体,如大于1mm的电解质。例如,在室温,在该组合物中,硫酸钠的浓度接近其饱和浓度是不符合要求的。
悬浮的杀生或农药的有效物质可以包括一种或多种农药或杀生剂,如选择性的或广谱性的除草剂,脱叶剂、杀虫剂、杀螨剂、杀软体动物剂、杀线虫剂和其它杀蠕虫剂、杀菌剂、杀细菌剂、杀病毒剂和其它农药、植物营养剂或生长或发育调节剂。
悬浮物质的微粒或液滴大小可以有很大的变化。它能够稳定悬浮的最大尺寸取决于悬浮相的密度和悬浮介质的流动点。然而,从实际出发,我们选取的最大微粒小于1mm,较好的小于500微米,最好平均微粒的大小多数颗粒在0.1至250微米之间,如0.5至200微米,特别是1至100微米的范围。平均微粒大小常常在1和10微米之间。
这里有效物质是低熔点的固体,它有时可需要结合少量熔点抑制剂,在制造或储存该组合物时抑制相变。这种变化会产生不稳定性。
适宜的有效物质包括甜菜呋、甲二威灵、棉隆、代森锰锌、亚甲基双硫代氰酸酯、胺三氮螨和嗪胺灵。
悬浮相的比例按重量计算约为1%和80%之间,通常在10%到60%之间变化。一般说来从经济上考虑选取不失去流动性的数量多的农药,如30%到50%。在21秒-1切力下悬浮剂的粘度一般在0.2和50帕斯卡秒之间,如0.2至5帕斯卡秒,较好的是0.2至3帕斯卡秒,特别是在0.2至1.5帕斯卡秒。我们通常选取在136秒-1下测得悬浮剂粘度可在0.05至10帕斯卡秒范围内,较好地在0.08至5帕斯卡秒,如在0.1至2帕斯卡秒间,最好是0.15至1帕斯卡秒。
许多在水中之杀生剂或农药的有效物质悬浮剂由于悬浮的物质与含水分质和/或制剂配方中的其它成分之间相互作用而缺乏稳定性。例如胺三氮螨悬浮剂存在晶体生长的严重问题,这是由于它在含水介质中轻微溶解性引起的。而在作物上使用时,许多组协同或互补作用的农药在以含水浓缩物形态存在时化学上是不相容的。
根据一个具体优选的实施例,本发明提供了一种保护在水剂中悬浮农药而不受含水的悬浮介质或制剂中其它成分相互作用的方法。我们发现,象水溶性成膜聚合物这样的成囊剂中胶囊化的农药可以稳定地悬浮在含有水结构的液体中,而且使我们惊奇的是,在贮藏上保留其实用程度的稳定性。
在水溶性成膜聚合物中和在树脂中的微囊化作用是使许多种敏感成分结合到药剂上或酶上并防止它们在空气中贮存时变质的已知技术。这样的胶囊可以通常的方法在含水介质中使用,它们在使用前即将胶囊溶解并释放出有效成分。因此,从表面上看,不能使用这种胶囊提供在含水介质中的贮存保护。
我们确信,在结构的液体水溶性胶囊的令人吃惊的稳定性是由于后者较高的电解质含量。电解质需要与表面活性剂作用,它通常把一种悬浮的不溶微粒变成球状和层状的结构。
一种结构的液体洗涤剂的悬浮性质有助于防止农药的凝聚和沉积。我们相信电解质也防止了水溶性胶囊的溶解作用。而胶囊保护农药一直到制剂为使用而被稀释,当电解质稀释到足以使胶囊溶解并释放出农药时。
根据一种具体的实施方案,本发明提供了一种含水基质的农药制剂。该制剂包含一种水悬浮介质,该介质悬浮一种水溶性成囊剂凝聚或胶囊化的杀生剂的和农药的有效物质的颗粒和液滴,水溶性成囊剂在所述的含水悬浮介质中是不溶的。较好的含水悬浮介质包含一种表面活性剂和足够多的电解质使表面活性剂形成一种能负载悬浮的固体微粒的结构并防止胶囊壳的溶解作用。
这里胶囊剂在常温下是固体或在固体颗粒里能够吸收,微囊化的农药可以通过如颗粒化或造粒化制成。在流动床或盘状粒化器中可以把农药颗粒用熔化的成囊剂或浓缩的成囊剂水溶液包裹,该成囊剂水溶液蒸发后留下胶囊膜。无论是在熔化的或是在含水成囊剂中分散的农药,都可以造粒或喷雾干燥,各自生成细小的,胶囊化的颗粒。这种技术是公知的。然而,涂膜或造粒的缺点是获得理想的胶囊有时是困难的。在涂膜全过程中,任何停顿都能使涂过膜的农药颗粒当加入到含水悬浮介质中时会迅速地变质。
根据一种优选的具体方案,本发明提供了一种使农药胶囊化或凝聚化悬浮在一种含水结构表面活性剂中的方法,它含有溶解的电解质,还有附加的成囊剂水溶液。农药和成囊剂可以在此之前,在此之后或者与电解质同时加到含水的表面活性剂中。
根据本发明,所用的成囊剂可以是一种聚合物或树胶的水溶性有机成膜大分子。我们优选使用一种水溶性的聚乙烯吡咯烷酮。我们也能使用聚乙烯醇,一种象羧甲基纤维素,甲基纤维素或羟甲基纤维素这样的纤维素衍生物,一种象瓜耳树胶、安息香树胶、黄蓍胶、阿拉伯胶或合金欢胶这样的树胶,一种象酪蛋白、明胶或清蛋白这样的蛋白质,一种象淀粉、葡萄糖、半乳糖、直链淀粉、支链淀粉这样的碳水化合物,或象聚丙烯酯或聚马来酸酯这样的聚羧酯酸。成囊剂最好不是表面活性剂或聚乙二醇。
最好水溶性成囊剂是可以被电解质沉淀的聚合物,在农药颗粒周围形成一种固体凝胶状或粘性膜或粘结层。成囊剂溶液的浓度按重量计算占0.5%直到饱和。
举例来说,象聚乙烯吡咯烷酮这样的聚合物用作成囊剂,我们选取分子量是从10,000到1,500,000,例如15,000到1,000,000较好的是20,000至900,000,特别是25,000至800,000。如果用聚乙烯醇,我们选取的聚合物分子量是18,000至140,000,最好是50,000至120,000,例如80,000至100,000。根据本发明,最好所用的聚乙烯醇是一种部分水解的聚乙烯基低级(例如C1-C4)的羧酸酯,尤其是聚乙烯基乙酸酯,其水解程度大于25%,小于95%,尤其是50%至90%,最好是60%至80%,例如70%至75%。
在不溶于含水表面活性剂的硅油,凡士林或石油明油这样的疏水性液体中,也可能使农药微粒胶囊化。这种疏水性成囊剂可用于某些农药,它们在叶片上的停留时间和活性由于疏水性液体介质的存在而增强。
在硅油这样的疏水性液体中,可以分散固体或液体的农药并且这种分散液体本身可以分散在含水表面活性剂介质中。
胶囊化的农药体系最好微粒直径平均为2μ至2.5mm,尤其是5μ至1mm,所希望的是10μ至700μ,最好是100μ至500μ。我们优选100μ至350μ范围的分散微粒。
被保护的微粒按重量计算一般包含整个微粒重量的0.5%至90%的成囊剂,较好的是1%至50%如2%至20%。
由于凝聚或在悬浮的微晶之间的类似作用,稳定性会受至影响。这可以使象聚电解质这样的位阻抑制剂避免。例如可以使用按重量计算比例小的聚丙酸盐(酯)或马来酸酐的共聚物,如0.1%至10%,较好的0.5%到5%,特别是1%到4%。
我们选取本发明的悬浮剂具有低的发泡性。这可以通过选用固有低发泡性能的表面活性剂来实现,一般选用硅油防泡剂,磷酸酯,脂肪醇或烃油这类的防泡剂。典型的防泡剂需要按重量计算百分比浓度是0.1%至5%。
该组合物可任意地包括象羧甲基纤维素或聚乙烯吡咯烷酮这样的悬浮剂,例如,按重量计算百分比为0.1%到5%,较好地是0.5%到2%的数量。
该组合物也可任意地含有增效剂、可溶性杀生剂,植物营养剂,植物生长调节剂、防腐剂、缓冲剂、防冻剂、着色剂和香料。
我们选取该组合物中不含任何有机溶剂,即不含低级的单或多羟基的醇、酮,聚醚这样与水混溶的溶剂,或是象芳香烃这种非水混溶性的溶剂,也不含任何象尿素、苯磺酸酯或低级烷基苯磺酸盐(酯)这样的水溶性助长剂。溶剂和水溶性助长剂可能对表面活性剂的结构有干扰,且需要使用实际增加表面活性剂和/或电解质的用量。同时它们也增加了制剂成本,而一般却没有增加制剂特性。芳香性溶剂是另一种有毒性而不受欢迎的溶剂。如果它们都存在的话我们选取溶剂和水溶助长剂各自的比例按重量计算小于10%,较好的是小于5%,最优选的是小于1%,例如小于0.5%,通常小于0.1%,更一般地小于0.05%。
与此类似,我们不选取树胶这样的聚合增稠剂,或它以浓度小于5%,最好是小于0.5%存在,因为它们一般对于稳定组合物不是必要的,而且因为它们还增加了悬浮剂的成本和粘度。
本发明可以用下述实施例来举例说明,其中的有的百分数都是以整个重量为基准的重量百分数计算。
实施例1
椰子单乙醇胺化物 (C12C14) 2.1%
直链烷基苯磺酸盐 (C12) 5.2%
水 51.4%
硅氧烷消泡剂 0.1%
甜菜呋 40.0%
硝酸钠 1.2%
实施例2
直链烷基苯磺酸盐(酯) (C12) 4.9%
十二烷基3摩尔乙氧基磺酸钠 1.7%
水 49.7%
硅氧烷消泡剂 0.1%
甜菜呋 40%
硝酸钠 3.6%
实施例3
椰子二乙醇胺化物 (C12C14) 3%
直链烷基苯磺酸盐(酯) (C12) 3%
水 50.9%
硅氧烷消泡剂 0.1%
硝酸钠 3%
甜菜呋 40%
实施例4
椰子二乙醇胺化物 (C12C14) 3%
直链烷基苯磺酸盐(酯) 3%
硅氧烷消泡剂 0.1%
水 49.9%
聚丙烯酸钠(m,W2,500) 1%
硝酸钠 3%
甜菜呋 40%
实施例5
直链烷基二乙醇胺化物 1.3%
椰子二乙醇胺化物 5.0%
十二烷基3摩尔乙氧基硫酸钠 0.4%
NaHCO34.6%
硅氧烷消泡剂 0.1%
莠去津 30%
水 58.6%
实施例6
胺三氮螨 50%
C10-14直链烷基苯磺酸钠30%水溶液 8.1%
十二烷基3摩尔乙氧基硫酸钠70%水溶液 1.7%
聚乙烯吡咯烷酮 0.56%
碳酸钾 4%
硅氧烷消泡剂 0.04%
水 35.6%
在含水表面活性剂存在下,把胺三氮螨磨细到<5μ。搅拌下加入4%的聚合物水溶液。最后在搅拌下加入40%的碳酸盐的水溶液。
所有的实施例都形成均匀的、流动性的悬浮剂,它们很容易分散在水中形成相当稳定的可喷雾的分散体。
实施例4的储存性能特别优良,与实施例1,2和3相比有实质性的改进。
实施例6的储存性能是优越的,相比之下,由于晶体的迅速生长,没有PVP的胺三氮螨悬浮剂是不稳定的。
实施例7
直链C12烷基苯磺酸钠 5.33%
C12-14烷基3摩尔乙氧基硫酸钠 1.87%
硅氧烷消泡剂 0.1%
碳酸氢钠 2.6%
45%的聚羧酸(MW2,700)水溶液 2.22%
甜菜呋 45%
水 加到100%
溶变性好
在室温和50℃可以稳定3个月
在3F/T循环之后变稠
很好的分散性
实施例8
C12直链烷基苯磺酸钠 5.33%
C12-14烷基3摩尔乙氧基硫酸钠 1.87%
硅氧烷消泡剂 0.1%
碳酸氢钠 2.6%
45%聚羧酸(MW<2,700)水溶液 2.22%
嗪胺灵 45%
水 加到100%
流变性好
室温下稳定3个月
50℃下发生增稠
在F/T循环后发生浓缩
很好的分散性
实施例9
异丙胺直链C12烷基苯磺酸盐 6.3%
硅氧烷消泡 0.1%
碳酸氢钠 6.4%
聚乙烯醇 1.0%
甲二威灵 20%
水 加到100%
所有的性能都优越
实施例10
直链C12烷基苯磺酸钠 6.0%
直链C12-13醇3摩尔乙氧基化物 6.0%
硫酸氢钠 4.8%
甲二威灵 20%
水 加到100%
所有的性能都优越
实施例11
壬基苯基乙氧基化物 4.2%
异丙基胺直链C12烷基苯磺酸钠 3.9%
硅氧烷消泡剂 0.1%
硫酸氢钠 6.7%
甲二威灵 16%
水 加至100%
所有的性能都优越
实施例12
椰子二乙醇胺化物 2.6%
直链C12烷基苯磺酸钠 2.6%
硅氧烷消泡剂 0.1%
硝酸钠 3.96%
代森锰锌 1%
水 加至100%
流变性能优越
50℃下储存增稠
实施例13
直链C12醇3摩尔乙氧基化物 3%
直链C12烷基苯磺酸钠 12%
磷酸二氢钠 2.5%
亚甲基二硫代氰酸盐(酯) 30%
45%聚羧酸(M2,700)水溶液 2.22%
水 加至100%
所有的性能都优越。
实施例14
直链C12烷基苯磺酸钠 8%
直链C12-13醇3摩尔乙氧基化物 1%
三聚磷酸钠 4%
棉隆 25%
水 加至100%
Claims (14)
1、一种包括含水结构表面活性剂的悬浮剂,其中悬浮一种基本上不溶于水的或微溶于水的杀生剂或农药的颗粒或微液滴,表面活性剂与所述有效物质的重量比小于20∶1。
2、根据权利要求1的悬浮剂,包括水,能充分提供一种固体悬浮结构的表面活性剂和形成所述结构所充分溶解的表面活性-减溶性电解质。
3、根据权利要求1或2,悬浮剂中所说的结构是一种层状结构。
4、根据权利要求1或2,悬浮剂中所说的结构是球状结构。
5、根据前述的任意一个权利要求,它含有按重量计算5至35%的表面活性剂。
6、根据前述的任意一个权利要求,其中所说的表面活性剂包括一种烷基苯磺酸钠。
7、根据前述的任意一个权利要求,其中表面活性剂是一种烷基单或双乙醇胺化物。
8、根据前述的任意一个权利要求,其中表面活性包括单烷基醚硫酸盐(酯)。
9、根据前述的任意一个权利要求,其中表面活性剂是一种乙氧基化醇。
10、根据前述2到9中的任意一个权利要求,其中所说的电解质存在浓度按重量计算是5%至12%。
11、根据前述的任意一个权利要求,其中悬浮的活性物质平均微粒大小是0.5至200微米。
12、根据前述的任意一个权利要求,其中的有效活性物质是甜菜呋、甲二威灵、棉隆、代森锰锌、亚甲基双硫代氰酸酯,胺三氮螨和嗪胺灵。
13、根据前述的任意一个权利要求,按重量计算所述的悬浮活性物质占整个组分总重10%到60%。
14、根据权利要求1的悬浮剂,其中所说的悬浮颗粒或微液滴是用一种水溶性成囊剂胶囊化或凝聚的杀生或农药的有效物质,它在所述的水悬浮介质中不溶。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103651337A (zh) * | 2012-09-24 | 2014-03-26 | 宜德雅(北京)科技有限公司 | 一种杀菌增效悬浮剂组合物 |
| CN103651338A (zh) * | 2012-09-24 | 2014-03-26 | 宜德雅(北京)科技有限公司 | 一种杀菌增效组合物 |
| CN113226023A (zh) * | 2018-12-28 | 2021-08-06 | 四国畜牧养殖设备株式会社 | 含有杀有害生物剂的散布剂 |
| US12268211B2 (en) | 2018-12-28 | 2025-04-08 | Shikoku-Cage Co., Ltd. | Spraying agent comprising pesticide |
| CN115190763A (zh) * | 2020-03-27 | 2022-10-14 | 陶氏环球技术有限责任公司 | 噻唑膦杀虫剂调配物 |
| CN119344325A (zh) * | 2024-09-13 | 2025-01-24 | 顺毅股份有限公司 | 一种棉隆悬浮剂制剂及其制备方法 |
| CN119344325B (zh) * | 2024-09-13 | 2025-09-30 | 顺毅股份有限公司 | 一种棉隆悬浮剂制剂及其制备方法 |
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