CN102100229A - Pesticide micro-capsule granules and preparation method thereof - Google Patents

Pesticide micro-capsule granules and preparation method thereof Download PDF

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CN102100229A
CN102100229A CN 200910201233 CN200910201233A CN102100229A CN 102100229 A CN102100229 A CN 102100229A CN 200910201233 CN200910201233 CN 200910201233 CN 200910201233 A CN200910201233 A CN 200910201233A CN 102100229 A CN102100229 A CN 102100229A
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pesticide
granules
capsule
material
micro
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CN 200910201233
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Chinese (zh)
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仲苏林
吴建兰
曹新梅
曹雄飞
章东生
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南通联农农药制剂研究开发有限公司
联合国南通农药剂型开发中心
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Abstract

The invention discloses micro-capsule granules and a preparation method thereof. The pesticide micro-capsule granules mainly comprise the following ingredients in percentage by weight: 5 to 75 percent of pesticide active ingredient, 1 to 10 percent of capsule wall material, 1 to 3 percent of wetting agent, 3 to 8 percent of dispersing agent, 0 to 10 percent of adjuvant and 10 percent of carrier filler. The preparation method comprises the following steps of: wrapping a micro-capsule by using active pesticide as a capsule core and using a high molecular material as a capsule shell material; preparing a micro-capsule suspending agent CS from water serving as a basic dispersant medium; and drying the micro-capsule suspending agent CS to prepare granules by using drying equipment to form a pesticide new formulation of the micro-capsule granules with control release effect. The invention has the advantages that: the pesticide micro-capsules are more environmentally-friendly and safer for a human body, have good control and prevention effects on targeted pests and are convenient to use.

Description

农药微囊颗粒剂及其制备方法 Pesticide microcapsule granule and preparation method

技术领域 FIELD

[0001] 本发明属于农药剂型加工领域,尤其涉及一种农药微囊颗粒剂及其制备方法。 [0001] The present invention belongs to the field of pesticide formulations and processing, in particular, it relates to a pesticide microcapsule granule and preparation method thereof.

背景技术 Background technique

[0002] 微胶囊粒剂(Encapsulated Granule, CG)是以高分子材料作为囊壁或囊膜,通过化学、物理或物理化学的方法,将作为囊心的农药活性物质包裹起来,形成一种具有半渗透性囊膜的微型胶囊,再将多个微胶囊集结在一起而形成的的固体颗粒。 [0002] microencapsulated granules (Encapsulated Granule, CG) is a polymer material as the capsule wall, or by chemical, physical or physico-chemical methods, wrapped up as a pesticidally active substance capsule core is formed having semipermeable microcapsules of the capsule, then a plurality of microcapsules gathered together to form solid particles. 囊芯中的活性物质在控制的条件下缓慢释放,以满足合适的防效要求。 Capsule core slow release of the active substance under controlled conditions, to meet the requirements of a suitable control effect. 微胶囊粒剂可用水用水稀释后喷雾使用,用水稀释后成悬浮液使用,悬浮液平均粒径可在2-50微米范围内,是典型的农药控制释放剂;同时微胶囊粒剂也可以深加工做为颗粒剂直接使用,用于土壤中有害生物的控制。 Microencapsulated granules can be diluted with water spraying use, after dilution with water into a suspension, the suspension may be in the average particle diameter of 2-50 microns, a typical controlled release pesticide agents; granules while the microcapsules may be further processing as granules used directly for the control of harmful organisms in the soil. 相对于其他剂型,它具备了微胶囊剂CS和水分散粒剂WDG的双重特点,有如下优点: Compared to other dosage forms, it has the characteristics of both CS and microcapsules of WDG water dispersible granules, has the following advantages:

[0003] (1)由于对有效成分的控制释放有着较长的持效期;减少施药的次数 [0003] (1) Because of controlled release of the active ingredient has a long persistence; reduce the number of administration

[0004] (2)减少了有机溶剂(甲苯、二甲苯等)的使用,从而对环境更加友好; [0004] (2) reducing the use of organic solvents (toluene, xylene, etc.), and thus more environmentally friendly;

[0005] (3)包裹在囊壳材料后有效成分在环境中分解率大大降低; [0005] (3) wrapping the decomposition rate of the active ingredient is greatly reduced in the environment after the capsule shell material;

[0006] (4)减少由于蒸气挥发带来有效成分的损失,减少对作物的药害; [0006] (4) reduce the vapor loss of active ingredients caused volatilization, reducing injury to crops;

[0007] (5)没有粉尘飞扬,对作业者安全,并且可以使高毒品种低毒化; [0007] (5) no dust flying, the safety of the operator, and may be of the high toxicity of the drug species;

[0008] (6)有效成分含量高,产品相对密度大,体积小,便于包装、贮存和运输; [0008] (6) high active ingredient content, high relative density, small size, ease of packaging, storage and transportation;

[0009] (7)贮存稳定性和物理化学稳定性较好。 [0009] (7) good storage stability and physicochemical stability.

[0010] 目前国内微胶囊悬浮剂是一个刚起步的剂型,而微囊颗粒剂产品基本空白。 [0010] At present, a capsule suspension is a start-up dosage form, granules and microcapsules basic products blank. 微囊粒剂和微囊悬浮剂的比较,由于微囊悬浮剂产品基本上是液态形式,因此产品存在着以下缺点: Comparison of encapsulated granules and the capsule suspension, capsule suspensions since the product is substantially liquid form, so there is the disadvantage that the product:

[0011] (1)存储的稳定性不佳,容易分层结底; [0011] Poor (1) storage stability and ease of the bottom hierarchical structure;

[0012] (2)化学稳定性较差; Poor [0012] (2) chemical stability;

[0013] (3)不易运输,且包装成本高; [0013] (3) easy to transport, and the high packaging costs;

[0014] (4)使用时要稀释喷雾,多用劳动力。 [0014] (4) when used to dilute a spray, the use of labor.

发明内容 SUMMARY

[0015] 本发明是为了克服现有技术存在的上述缺点,而提供的一种农药微囊颗粒剂及其制备方法。 [0015] The present invention is to overcome the above disadvantages of the prior art, while a pesticide microcapsule granule and preparation method provided. 本发明通过新的工艺路线,以农药为囊芯,以高分子材料为囊壳材料进行包裹的微胶囊,并以水为基础分散介质制成微胶囊悬浮剂CS,然后在通过干燥设备将微囊悬浮剂CS干燥制粒,生产制备的农药微囊颗粒剂具有控制释放作用,对于调整我国农药制剂产品结构的更新换代和促进社会生态效益的提高有着显著作用。 The invention of new process routes to pesticide as core, encapsulated in a polymer material for the capsule shell material of the microcapsule, and a water-based dispersion medium microcapsules suspensions the CS, and then dried by a micro device capsule suspensions CS dry granulation, pesticide granules prepared microcapsule production of controlled release effect, preparations for the upgrading of product structure adjustment of China's pesticide and promote eco-efficient society has a significant role.

[0016] 为了实现上述目的,本发明农药微囊颗粒剂,其特点是,主要含有以下重量百分比的成分:农药有效成分5〜75% ;囊壁材料1〜10% ;润湿剂1〜3% ;分散剂3〜8% ;辅助剂0〜10% ;载体填料补足总重量百分比为100%。 [0016] To achieve the above object, the present invention is the pesticide microcapsule granules, characterized by, comprising the following weight percentages of the major components: 5~75% pesticide active ingredient; 1~10% wall material; wetting agent 1 ~ 3 %; dispersant 3~8%; 0 ~ 10% adjuvant; carrier filler make up 100% by weight of the total.

[0017] 上述农药微囊颗粒剂,其中,所述的可适用于该法制备农药微囊颗粒剂的原药成分包括:氟氯氰菊酯、毒死蜱、高效氰氰菊酯、顺式氯氰菊酯、苯醚菊酯、除虫菊素、吡虫啉、人工合成的引诱剂、氰戊菊酯、马拉硫磷、杀螟硫磷、甲基对硫磷、乙基对硫磷、毒死蜱、辛硫磷、阿维菌素、丙线磷、苯线磷、二嗪磷、丁硫克百威、硫丹、阿维菌素、杀扑磷、哒螨灵、阿维菌素、氟硅唑、丙环唑、腈菌唑、苯醚甲环唑、三唑酮、甲草胺、乙草胺、丁草胺、野麦畏、二甲戊灵、异恶草松、氟乐灵、仲丁灵。 [0017] The granule pesticide microcapsule, wherein the microcapsule is applied pesticide granules prepared in the legal original drug composition comprising: cyfluthrin, chlorpyrifos, efficient cyanuric cyhalothrin, cypermethrin, chrysanthemum ether esters, pyrethrin, imidacloprid, synthetic attractants, fenvalerate, malathion, fenitrothion, methyl parathion, ethyl parathion, chlorpyrifos, phoxim, avermectin , Ethoprophos, fenamiphos, diazinon, carbosulfan, endosulfan, abamectin, methidathion, pyridaben, avermectin, flusilazole, propiconazole, myclobutanil thiazole, oxazole difenoconazole, triadimefon, alachlor, acetochlor, butachlor, triallate, pendimethalin, clomazone, trifluralin, butralin.

[0018] 上述农药微囊颗粒剂,其中,所述的囊壁材料为合成聚脲树脂高分子材料。 [0018] The microcapsules of pesticide granules, wherein said wall material is a polyurea synthetic resin polymer material.

[0019] 上述农药微囊颗粒剂,其中,所述的润湿剂选自十二烷基硫酸钠、壬基酚聚氧乙烯、烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物硫酸盐磷酸盐、苯乙烯苯酚甲醛树脂聚氧乙烯醚磷酸酯盐、苯乙烯基酚聚氧乙烯聚氧丙烯醚、烷基萘甲醛缩合物磺酸盐、烷基丁二酸酯磺酸盐、斯盘SPAN、土温TWEEN中的两种或者三种以上的组合使用。 [0019] The microcapsules of pesticide granules, wherein said wetting agent is selected from sodium lauryl sulphate, nonylphenol, alkylphenol formaldehyde condensate sulfates, alkylphenol ethylene oxide ether sulfates phosphates formaldehyde condensates, phenol-formaldehyde resin, a styrene polyoxyethylene ether phosphate ester salts, polyoxyethylene styryl phenol polyoxypropylene ethers, alkyl naphthalene sulfonate formaldehyde condensate, alkyl succinic ester sulfonate, Span the SPAN, TWEEN two kinds of soil temperature, or use a combination of more than three.

[0020] 上述农药微囊颗粒剂,其中,所述的分散剂选自萘磺酸钠甲醛缩合物、三苯乙烯基酚聚氧乙烯醚类和衍生物酯类、脂肪醇聚氧乙烯醚类、烷基酚聚氧乙烯醚类、高分子EO-PO 嵌段共聚物、木质素磺酸盐、烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物硫酸盐磷酸盐、苯乙烯苯酚甲醛树脂聚氧乙烯醚磷酸酯盐、苯乙烯基酚聚氧乙烯聚氧丙烯醚、烷基萘甲醛缩合物磺酸盐、高分子疏型的支装共聚物、聚合羧酸盐类中的两种或者三种以上的组合使用。 [0020] The microcapsules of pesticide granules, wherein said dispersant is selected from naphthalene sulfonate formaldehyde condensate, polyoxyethylene tristyrylphenol ether esters and derivatives, fatty alcohol polyoxyethylene ether , polyoxyethylene alkylphenol ethers, EO-PO block copolymer, polymer, lignin sulfonates, polyoxyethylene alkyl phenol formaldehyde condensate sulfates, alkylphenol ether sulfates formaldehyde condensate phosphates, phenol formaldehyde resin, a styrene polyoxyethylene ether phosphate ester salts, polyoxyethylene styryl phenol polyoxypropylene ethers, alkyl naphthalene sulfonate formaldehyde condensates, thinning polymer sticks type copolymer, carboxymethyl polymerization two or three or more acid salts in combination.

[0021] 上述农药微囊颗粒剂,其中,所述的载体填料选自包括改性水溶淀粉、纤维素醚及其衍生物、硅酸镁铝、高龄土、硅藻土、凹凸棒土、葡萄糖、轻质碳酸钙、白炭黑、无机盐中的一种。 [0021] The microcapsules of pesticide granules, wherein said carrier comprises a modified water-soluble filler is selected from starch, cellulose ethers and derivatives thereof, magnesium aluminum silicate, kaolin, diatomaceous earth, attapulgite, glucose , calcium carbonate, silica, an inorganic salt of one.

[0022] 上述农药微囊颗粒剂,其中,所述的辅助剂选自粘结剂、崩解剂、PH调节剂、杀菌防腐剂、消泡剂中的一种或几种的组合;其中:所述的粘结剂选用聚乙烯醇、明胶、阿拉伯胶、 黄原胶、聚丙烯酸钠、海藻酸钠、淀粉、纤维素及其衍生物,优选纤维素及其纤维素衍生物的一种,其占总重量百分比的0. 1〜2% ;崩解剂选自于硅酸镁铝、聚乙二醇PEG、改性淀粉、 无机盐、白碳黑、硅胶的一种,其占总重量百分比的2〜5% ;所述的PH酸碱调节剂为冰醋酸、盐酸、氨水、乙醇胺、三乙醇胺中的一种,其占总重量百分比的0. 1〜2% ;所述的杀菌防腐剂为:山梨酸钾、苯甲酸钠、甲醛、异噻唑啉酮类中的一种,其占总重量百分比的0. 〜 0.5% ;所述消泡剂:天然油脂、聚醚类消泡剂、高碳醇、有机硅消泡剂的一种,其占总重量百分比的0. 1〜1. 5%。 [0022] The microcapsules of pesticide granules, wherein the adjuvants are selected from binders, disintegrating agents, PH adjusting agent, antiseptic, defoaming agent, or a combination of several of; wherein: the selection of a polyvinyl alcohol binder a gelatin, acacia gum, xanthan gum, sodium polyacrylate, sodium alginate, starch, cellulose and derivatives thereof, preferably cellulose and cellulose derivatives, its total 0. 1 to 2% by weight; the disintegrant is selected from magnesium aluminum silicate, polyethylene glycol PEG, modified starch, inorganic salt, white carbon black, a silica gel, which is the total weight 2 ~ 5% percentage; the PH adjusting agent is glacial acetic acid, hydrochloric acid, ammonia, ethanolamine, triethanolamine one which total 0. 1 to 2% by weight; the antiseptic agents are: potassium sorbate, sodium benzoate, formaldehyde, isothiazole oxazoline for ketone in which 0.5 weight percent of the total to 0.5%; the defoaming agent: natural oils, polyether-based defoaming agent, high carbon alcohol, a silicone antifoaming agent, 0.5 weight percent of its total 1~1. 5%.

[0023] 上述农药微囊颗粒剂,其中,所述的水为去离子水或者蒸馏水。 [0023] The microcapsules of pesticide granules, wherein said water is deionized or distilled water.

[0024] 本发明还公开了一种上述的原料组分和比例,包括以下步骤: [0024] The present invention also discloses a feed components and ratios described above, comprising the steps of:

[0025] 第一步,通过农药微囊化技术,采用界面聚合法制备得到农药微囊悬浮剂或者微囊粉体; [0025] The first step, by microencapsulation pesticide, by interfacial polymerization of pesticide microcapsule suspension prepared microcapsules or powder;

[0026] 第二步,通过喷雾干燥干燥制粒或者挤压制粒干燥,从而得到农药微囊颗粒剂。 [0026] The second step, by spray drying granulation or extrusion granulation drying and dried to obtain a microencapsulated pesticide granules.

[0027] 上述农药微囊颗粒剂的制备方法,其中, Preparation [0027] The method of the above-described microcapsules of pesticide granules, wherein

[0028] 1、首先制备农药微囊悬浮剂,包括以下步骤:: [0028] 1, pesticide microcapsule suspension is first prepared, comprising the steps of ::

[0029] 1-1、将原药加热熔融加入适量的油相成囊材料搅拌均勻得到油相; [0029] 1-1, the drug is heated and melted original amount of oil added to stir the bladder material complementary obtain an oil phase;

[0030] 1-2、在水中预先加入润湿剂、分散剂搅拌均勻,然后加入预先配置好的油相,高速均化形成稳定水包油乳液;[0031] 1-3、降低转速,加入囊壁材料单体多元胺或者多元醇水溶液参加界面聚合反应形成聚脲树脂囊壁材料,反应温度控制在20°C〜80°C内,保持2小时〜24小时,使囊壁材料固化成囊; [0030] 1-2, a wetting agent in water in advance was added, stirred uniformly dispersing agent, then adding the oil phase pre-configured, high-speed homogenizer to form a stable oil in water emulsion; [0031] 1-3, lower speed, was added monomeric polyamine wall material or polyol to form an aqueous solution of participation interfacial polymerization polyurea resin wall material, the reaction temperature is controlled within 20 ° C~80 ° C, 2 hours ~ 24 hours, the material is cured into the bladder wall ;

[0032] 1-4、待成囊材料完全固化成囊后,加入PH酸碱调节剂,调节至所需PH值范围内, 再加入适量分散剂及黏结剂、消泡剂等辅助剂,搅拌均勻即制成农药微囊悬浮剂; [0032] 1-4, to be fully cured bladder material into the capsule, pH adjusting agent added PH, PH adjusted to the desired value within the range, then add the appropriate amount of dispersant and binder, adjuvants such as defoamers, stirring i.e. made uniform pesticide microcapsule suspension;

[0033] 上述1-1〜1-4步骤中工艺过程均在常压状态下实施完成; [0033] The process steps 1-1~1-4 embodiment are carried out at normal pressure;

[0034] 2、然后将农药微囊悬浮剂通过干燥造粒得到微囊颗粒剂,所述的干燥造粒主要通过挤压造粒法或喷雾干燥法两种造粒干燥方式得到微囊颗粒剂,其中: [0034] 2, then drying the granulated pesticide microcapsule to give microcapsules by suspending granules, the dried granules extrusion granulation or spray drying method employs two ways granulated and dried to obtain granules microencapsulated primarily by ,among them:

[0035] 挤压造粒法是指通过载体填料对微囊悬浮剂进行吸附,然后加入润湿剂、分散剂、 崩解剂等辅助剂,再挤压造粒,最后通过沸腾干燥得到微囊粒剂; [0035] The extrusion granulation method is a capsule suspension for adsorption of filler through the carrier, and wetting agents, dispersing agents, disintegrating agents and adjuvants, and then extrusion granulation, and finally dried to obtain microcapsules by boiling granules;

[0036] 喷雾干燥法是指直接采用微囊悬浮剂料浆直接喷雾干燥制粒,最终得到微囊颗粒齐U;包括以下步骤: [0036] The spray drying method is a method using a capsule suspension directly spray-dried slurry directly granulated, microencapsulated granules finally obtained homogeneous U; comprising the steps of:

[0037] 2-1、首先将预先制备的微囊悬浮剂与分散剂、湿润剂、崩解剂和填料载体等一起搅拌均勻,调整其浓度和粘度,得到喷雾用的浆料; [0037] 2-1, a capsule suspension is first stirred with a dispersing agent previously prepared, wetting agents, disintegrating agents and the like together with carriers and fillers uniformly adjust the concentration and viscosity of the resulting slurry was spray;

[0038] 2-2、然后将浆料经喷嘴雾化成微小的液滴,射入喷雾容器内,热空气与喷射滴并流或逆流进入干燥器; [0038] 2-2, and then the slurry is atomized by the nozzle into fine droplets, enters a spray container, with a hot air current or countercurrent droplet jet into the dryer;

[0039] 2-3、干净的热空气与料浆在造粒设备内与物料混合并蒸发料浆中的水分,形成颗粒剂。 [0039] 2-3, a clean hot air mixed with the slurry in the granulation equipment and evaporated and the material moisture content in the slurry to form granules.

[0040] 本发明由于采用了以上的技术方案,其产生的技术效果是明显的: [0040] The present invention adopts the above technical solution, which produces a technical effect are obvious:

[0041] 1、农药微囊颗粒剂CG可减少传统制剂乳油中所使用的有机溶剂(甲苯、二甲苯等),对环境更加友好。 [0041] 1, granules of pesticide microcapsule formulation CG conventional emulsifiable concentrate can be reduced by using an organic solvent (toluene, xylene, etc.), more environmentally friendly.

[0042] 2、农药微囊颗粒剂CG,可有效降低制剂的毒性,对人体更加安全从而提高安全性。 [0042] 2, the CG pesticide microcapsule granules, can effectively reduce the toxicity of the formulation, safer to human body thereby improving safety.

[0043] 3、可对农药有效成分控制释放,因而有着较长的持效期,减少施药的次数,减少农药的使总用量;对标靶有害生物有着良好的控制与防治作用。 [0043] 3, it may control the release of pesticide active ingredients, and therefore has a long persistence, reduce the number of administration, reducing the total amount of pesticides; of the target pest control and have a good preventive effect.

[0044] 4、可用于土壤中有害生物的控制时直接使用,不需要兑水稀释,对于干旱缺水地区来说有效降低施药者的劳动强度,操作方便。 [0044] 4, it can be used for direct control of harmful organisms in the soil, does not require dilution watered, For dryland applicators effectively reduce the labor intensity, and easy to operate.

附图说明 BRIEF DESCRIPTION

[0045] 图1是本发明实施例中采用的ZPG-150型喷雾干燥机的造粒流程示意图。 [0045] FIG. 1 is a schematic flow diagram of granulated ZPG-150 type spray dryer employed in the embodiment of the present invention. 具体实施方式 detailed description

[0046] 本发明采用了一种低成本,便于工业化生产的农药微囊颗粒剂制备方法和工艺路线。 [0046] The present invention employs a low cost, ease of preparation and industrial production process route microencapsulated pesticide granules. 本发明采用高分子材料为囊壁材料,成囊的制备方法是界面聚合法。 The present invention is the use of polymer materials as shell material, as the balloon is prepared by interfacial polymerization. 通过上述方法制备农药微胶囊悬浮剂或者沉淀干燥成粉末,然后通过制粒过程得到微囊颗粒剂。 Pesticides or capsule suspensions prepared by the precipitation method described above was dried into a powder, microcapsules and granules obtained by the granulation process.

[0047] 本发明的配方组成以重量百分比含量如下: [0047] The formulations of the present invention is a composition in weight percent content as follows:

[0048] 农药有效成分5〜75%; [0048] 5~75% pesticide active ingredient;

[0049] 囊壁材料 1〜10%; [0049] The wall material 1~10%;

[0050] 润湿剂 1〜3%; [0050] 1 ~ 3% wetting agent;

[0051] 分散剂 3〜8%;[0052] 辅助剂 0〜10%; [0051] The dispersant 3~8%; [0052] 0 ~ 10% adjuvant;

[0053] 载体填料补足总重量百分比为100%。 [0053] The total weight percent of the carrier filler is made up to 100%.

[0054] 本发明农药微囊颗粒剂的农药有效成分包括氟氯氰菊酯、毒死蜱、高效氰氰菊酯、顺式氯氰菊酯、苯醚菊酯、除虫菊素、吡虫啉、人工合成的引诱剂、氰戊菊酯、马拉硫磷、杀螟硫磷、甲基对硫磷、乙基对硫磷、毒死蜱、辛硫磷、阿维菌素、丙线磷、苯线磷、二嗪磷、丁硫克百威、硫丹、阿维菌素、杀扑磷、哒螨灵、阿维菌素、氟硅唑、丙环唑、腈菌唑、苯醚甲环唑、三唑酮、甲草胺、乙草胺、丁草胺、野麦畏、二甲戊灵、异恶草松、氟乐灵、仲丁灵等。 [0054] The pesticide microcapsule pesticide active ingredient granules of the present invention include cyfluthrin, chlorpyrifos, efficient cyanuric cyhalothrin, cypermethrin, phenothrin, pyrethrin, imidacloprid, synthetic attractants, fenvalerate , malathion, fenitrothion, methyl parathion, ethyl parathion, chlorpyrifos, phoxim, avermectin, Ethoprophos, fenamiphos, diazinon, butylthio Kebai Wei, endosulfan, abamectin, methidathion, pyridaben, avermectin, flusilazole, propiconazole, myclobutanil, difenoconazole cyproconazole, triadimefon, alachlor, b alachlor, butachlor, triallate, pendimethalin, clomazone, trifluralin, butralin like.

[0055] 所述的囊壁材料主要包括天然或合成高分子材料,包括明胶、阿拉伯胶、、壳聚糖、 木质素、环糊精、聚乙烯醇、聚脲树脂、脲醛树脂和三聚氰胺甲醛树脂等,我们优选聚脲树脂。 [0055] The capsule wall material mainly comprising a natural or synthetic polymer materials include gelatin, acacia gum,, chitosan, lignin, cyclodextrin, polyvinyl alcohol, urea resins, urea resins, and melamine-formaldehyde resins etc., we prefer polyurea resin.

[0056] 所述的润湿剂选用十二烷基硫酸钠、壬基酚聚氧乙烯(NP系列)、烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物硫酸盐磷酸盐、苯乙烯苯酚甲醛树脂聚氧乙烯醚磷酸酯盐、苯乙烯基酚聚氧乙烯聚氧丙烯醚、烷基萘甲醛缩合物磺酸盐、烷基丁二酸酯磺酸盐、斯盘SPAN、土温TWEEN中的两种或者三种以上的组合使用。 Wetting agents [0056] The selection of sodium lauryl sulfate, nonylphenol (NP series), polyoxyethylene alkylphenol sulfate formaldehyde condensate, polyoxyethylene alkyl phenol formaldehyde condensate sulfates phosphates, phenol formaldehyde resin, a styrene polyoxyethylene ether phosphate ester salts, polyoxyethylene styryl phenol polyoxypropylene ethers, alkyl naphthalene sulfonate formaldehyde condensate, alkyl succinic ester sulfonate, Span SPAN, more than two or three in the soil temperature TWEEN combination.

[0057] 所述的分散剂选用萘磺酸钠甲醛缩合物、三苯乙烯基酚聚氧乙烯醚类和衍生物酯类、脂肪醇聚氧乙烯醚类、烷基酚聚氧乙烯醚类、高分子EO-PO嵌段共聚物、木质素磺酸盐、 烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物硫酸盐磷酸盐、苯乙烯苯酚甲醛树脂聚氧乙烯醚磷酸酯盐、苯乙烯基酚聚氧乙烯聚氧丙烯醚、烷基萘甲醛缩合物磺酸盐、高分子疏型的支装共聚物、聚合羧酸盐类中的两种或者三种以上的组合使用。 Dispersant [0057] The selection of naphthalene sulfonate formaldehyde condensate, polyoxyethylene tristyryl ether esters and phenol derivatives, polyoxyethylene fatty alcohol ethers, polyoxyethylene alkyl phenol ethers, polymer EO-PO block copolymers, lignin sulfonate, polyoxyethylene alkyl phenol formaldehyde condensate sulfates, alkylphenol ether sulfates phosphates formaldehyde condensate, a polyoxyethylene styrene phenol formaldehyde resin vinyl ether phosphate ester salts, polyoxyethylene styryl phenol polyoxypropylene ethers, alkyl naphthalene sulfonate formaldehyde condensates, thinning polymer sticks type copolymer, polymerizing two or three kinds of carboxylates the combination of the above.

[0058] 所述的辅助剂选自粘结剂、崩解剂、PH调节剂、杀菌防腐剂、消泡剂中的一种或几种的组合;其中: [0058] The adjuvants are selected from binders, disintegrating agents, PH adjusting agent, antiseptic, antifoaming agent in one or a combination of several of; wherein:

[0059] 所述的粘结剂选用聚乙烯醇、明胶、阿拉伯胶、黄原胶、聚丙烯酸钠、海藻酸钠、淀粉、纤维素及其衍生物,优选纤维素及其纤维素衍生物的一种,其占总重量百分比的0.1〜 2% ; [0059] Selection of the binder polyvinyl alcohol, gelatin, acacia gum, xanthan gum, sodium polyacrylate, sodium alginate, starch, cellulose and its derivatives, cellulose and cellulose derivative preferably one of which is the total weight percent of 0.1~ 2%;

[0060] 崩解剂选自于硅酸镁铝、聚乙二醇PEG、改性淀粉、无机盐、白碳黑、硅胶的一种,其占总重量百分比的2〜5% ; [0060] The disintegrant is selected from magnesium aluminum silicate, polyethylene glycol PEG, modified starch, inorganic salt, white carbon black, a silica which is 2 ~ 5% by weight of the total;

[0061] 所述的PH酸碱调节剂为冰醋酸、盐酸、氨水、乙醇胺、三乙醇胺中的一种,其占总重量百分比的0. 1〜2% ; [0061] PH pH adjustment and said agent is acetic acid, hydrochloric acid, ammonia, ethanolamine, triethanolamine one which total 0. 1 to 2% by weight;

[0062] 所述的杀菌防腐剂为:山梨酸钾、苯甲酸钠、甲醛、异噻唑啉酮类中的一种,其占总重量百分比的0. 〜0. 5% ; [0062] The antiseptic is: potassium sorbate, sodium benzoate, formaldehyde, isothiazole oxazoline for ketone in which 0.5 percent by weight of the total 5% ~ 0;.

[0063] 所述消泡剂:天然油脂、聚醚类消泡剂、高碳醇、有机硅消泡剂的一种,其占总重量百分比的0. 1〜1. 5% [0063] The defoaming agent: natural oils, polyether-based defoaming agent, higher alcohol, an organosilicon defoamer, 0.5 weight percent of its total 1~1 5%

[0064] 所述的水为去离子水或者蒸馏水。 [0064] the water is deionized or distilled water. 所述的载体填料选自包括改性水溶淀粉、纤维素醚及其衍生物、硅酸镁铝、高龄土、硅藻土、凹凸棒土、葡萄糖、轻质碳酸钙、白炭黑、无机盐中的一种。 Said carrier comprising a modified water-soluble filler is selected from starch, cellulose ethers and derivatives thereof, magnesium aluminum silicate, kaolin, diatomaceous earth, attapulgite, glucose, calcium carbonate, silica, an inorganic salt in kind.

[0065] 本发明实现微囊颗粒剂的工艺路线主要为两步:第一步,通过农药微囊化技术,制备得到农药微囊悬浮剂或者微囊粉体;第二步,通过干燥制粒或者挤压制粒,从而得到为囊颗粒剂。 [0065] The present invention implements routing microcapsule granules mainly two steps: first, by microencapsulation of pesticides, pesticide microcapsule suspension prepared microcapsules or powder; a second step, by dry granulation or an extrusion granulator, to obtain granules of the balloon.

[0066] 第一步、农药微囊悬浮剂的制备:[0067] 现有的农药微囊化的技术主要是三种工艺路线: [0066] The first step, preparation of agrochemicals Capsule Suspension: [0067] prior art microencapsulated pesticides are three main process routes:

[0068] 第一种是采用界面聚合法的路线,通常使用异氰酸酯(TDI)或者预聚体(MDI)与多元胺或者多元醇反应,形成聚脲树脂的囊壳材料。 [0068] The first is to use interfacial polymerization route, typically an isocyanate (TDI) or prepolymer (MDI) is reacted with a polyol or polyamine body, the capsule shell material is formed of polyurea resin.

[0069] 第二种采用原位聚合工艺路线,一般采用尿素-甲醛预聚体溶液成囊,通过控制加酸速度、加酸的方式、熟化的温度、溶液搅拌的速度等工艺参数控制,通过调节PH范围, 在催化作用下缩聚形成坚固不易渗透的微胶囊。 [0069] The second route situ polymerization process, generally use urea - formaldehyde prepolymer solution into the balloon, by controlling the speed of addition of acid, acid is added to control the process parameters embodiment, the curing temperature, the solution was stirred for speed, through PH adjustment range, the polycondensation to form a firm less permeable microcapsules under catalysis.

[0070] 第三种是复凝聚法制备工艺,在溶解的天然高分子材料(如明胶、阿拉伯胶)混合的水溶液中,通过调节PH使天然高分子材质因溶解度降低,自体系中凝聚成囊析出。 [0070] A third is a complex coacervation process, a mixed aqueous solution dissolving a natural polymer materials (such as gelatin, acacia) by dissolving a natural polymer materials to adjust the PH due to decreased solubility, condensed into the bladder from the system precipitation. 再加入固化剂,产生胺醛缩合反应,天然高分子交联成网状结构,保持微囊的形状成为微囊。 Adding a curing agent to produce the amine-aldehyde condensation, natural polymer cross-linked into a network structure to maintain the shape of the microcapsules become microcapsules. [0071 ] 本发明采用的界面聚合法制备微胶囊,此法是制备农药微胶囊最常用的方法,工艺稳定便于控制的优点。 [0071] The present invention employs the microcapsules prepared by interfacial polymerization, this method is most commonly used pesticide microcapsule preparation method, the advantages of ease of process control stability. 其工艺过程简述如下:将有效成分和适宜的高分子囊壁材料(单体)溶解在有机溶剂中,接着将油相在剪切条件下加入到含有合适的乳化剂和保护胶的水相溶液中,成水包油或油包水形式,根据需要控制一定的颗粒大小。 Which process is summarized as follows: The active ingredient and a suitable polymer wall material (monomer) is dissolved in an organic solvent, then adding the oil phase to water containing a suitable emulsifier and a protective colloid under shear conditions with solution, into water-in-oil-in-water form, according to the need to control a certain particle size. 并在水相中再加入另一种水溶性的囊壁材料,两种材料在油水界面发生反应,围绕含有活性物质的液滴形成高分子囊壁。 And the aqueous phase was added to another water-soluble wall material, the reaction occurs at the oil-water interface of two materials, to form a polymer wall around the droplets containing the active substance. 此方法一般能快速进行,形成的囊壁较规则均一,质地坚硬。 This method is generally rapid, more regular form a uniform wall, hard texture.

[0072] 本发明的具体做法是:根据本配方所提供的材料,微囊悬浮剂可以通过以下的工艺路线制备得到: [0072] Specifically the present invention is: according to the material provided in the present formulation, capsule suspensions can be prepared by the following process route:

[0073] 将原药加热熔融加入适量的异氰酸酯囊壁材料单体搅拌均勻油相; [0073] original drug is heated and melted adding an appropriate amount of an isocyanate wall material monomer Stir the oil phase;

[0074] 在水中预先加入润湿分散剂搅拌均勻,然后加入预先配置好的油相,高速均化形成稳定水包油乳液; [0074] The wetting and dispersing agent is previously added uniformly stirred in water, then adding the oil phase pre-configured, high-speed homogenizer to form a stable oil in water emulsion;

[0075] 降低转速,在适合的转速条件下,加入多元胺或者多元醇水溶液参加界面聚合反应形成聚脲树脂囊壁材料,反应温度升至一个合适的区间内,保持一段时间使囊壁材料固化成囊。 [0075] reducing the rotational speed, the rotational speed under suitable conditions, was added an aqueous solution of the polyol or polyamine to attend interfacial polymerization polyurea resin wall forming material, the reaction temperature was raised to within a suitable range, a period of time that the wall material is cured encysted. 待成囊材料完全固化成囊后,加入PH酸碱调节剂,调节至所需PH值范围内,加入适量分散剂、黏结剂、消泡剂等,搅拌均勻即制成微囊悬浮剂。 After the material into the capsular bag into a fully cured, pH adjusting agent added PH, PH adjusted to the desired value within the range, addition of an appropriate amount of dispersant, binder, antifoaming agents, i.e. formed capsule suspension was stirred uniformly.

[0076] 本发明的工艺过程均在常压状态下实施完成。 [0076] The process of the present invention are carried out at normal pressure embodiment.

[0077] 本发明所提及的成囊过程中聚合反应所控制的温度在30°C〜80°C,优选40°C ; [0077] The reaction temperature is controlled at 30 ° C~80 ° C, preferably 40 ° C according to the present invention is referred to the bladder during the polymerization;

[0078] 本发明成囊材料所需的固化时间在2小时〜24小时之间,优选8小时; [0078] The present invention to the time required for curing bladder material between two hours ~ 24 hours, preferably 8 hours;

[0079] 本发明所得到的微胶囊悬浮剂的粒度控制2um〜50um之间,具备了农药水悬浮剂的特点。 [0079] The obtained capsule suspension of the present invention to control the particle size between 2um~50um, has the characteristics of the pesticidal aqueous suspension.

[0080] 本发明的微囊悬浮剂含量可以在5%〜40%之间变动,根据其不同的用途制定不同的含量。 [0080] Capsule suspensions of the present invention, the content may be between 5% ~ 40% change for different contents according to their different uses. 该微囊悬浮剂同时也是一种可控制有效成分释放速度的剂型,可根据其用途,决定囊壳的厚度来控制释放速度,以达到所需的效果。 The microcapsule suspension is also a controlled release rate of the active ingredient dosage, according to their use, determine the thickness of the capsule to control the release rate to achieve the desired effect.

[0081] 第二步:将农药微囊悬浮剂通过造粒干燥得到微囊颗粒剂。 [0081] Second Step: The pesticide microcapsule suspension granulated and dried to obtain microcapsules by granules. 通常农药颗粒剂的造粒方法有:喷雾干燥造粒、流动床干燥造粒、冷冻干燥造粒、盘式造粒、挤压造粒、高速混合造粒、流动床造粒和压缩造粒等。 The method generally granulated pesticide granules are: spray-drying granulation, fluidized bed granulation drying, freeze-drying granulation, pan granulation, extrusion granulation, high-speed mixing granulator, fluid bed granulation and compression granulation . 本发明优选选喷雾干燥造粒法(具体指将制备好的微囊悬浮剂进行喷雾干燥造粒,得到微囊颗粒剂CG)与挤压造粒法。 Preferably selected from spray-drying granulation method of the present invention (specifically, the prepared microcapsule suspension was spray granulated and dried to obtain granules microencapsulated CG) with extrusion granulation method. 本发明主要通过以下两种造粒干燥方式得到微囊颗粒剂: The present invention microencapsulated granules obtained by the granulation was dried in two ways:

[0082] 1、喷雾干燥造粒法通过下面的步骤实现:首先将微囊悬浮剂与分散剂、湿润剂、崩解剂和填料载体等一起搅拌均勻,调整其浓度和黏度,得到喷雾用的浆料,然后将浆料经喷嘴雾化器成微小的液滴,射入喷雾塔内,热空气与喷射滴并流进入干燥塔。 [0082] 1, spray-drying granulation method implemented by the following steps: First, the microcapsule suspension was stirred together with dispersants, wetting agents, disintegrating agents, and even other fillers carrier, adjusting the concentration and viscosity, of the resulting spray the slurry, then the slurry through the atomizer nozzle into fine droplets, enters a spray tower, hot air jet flow into droplets and drying column. 微囊悬浮剂在高压泵的作用下进入雾化器(压力喷嘴)后在旋涡室内产生高速旋转,从喷嘴孔旋转喷出后形成球形雾滴。 After the microcapsule suspension into the atomizer (nozzle pressure) under the action of high-pressure pump to generate high-speed rotation in the vortex chamber, after the formation of spherical droplets discharged from the nozzle holes of rotation. 雾滴受热后表面水分迅速蒸发,干燥后形成空心微囊颗粒剂CG。 After the rapid evaporation of water droplet heated surface to form hollow microcapsules CG granules after drying. 或者, or,

[0083] 2、挤压造粒法:通过载体填料对微囊悬浮剂进行吸附,然后加入润湿剂、分散剂、 崩解剂等一起混合均勻,然后通过挤压造粒机造粒,最后通过沸腾干燥得到微囊粒剂CG。 [0083] 2, extrusion granulation method: the carrier by filling a capsule suspension for adsorption, followed by addition of wetting agents, dispersing agents, disintegrating agents and mixed together and then granulated by an extrusion granulator, and finally microcapsules obtained by boiling dried granules CG. 该法生产易于操作,能耗较低。 The production of easy operation and low power consumption.

[0084] 为了更好的说明本发明技术,现通过以下具体实例进一步说明,但不仅限于此: [0084] In order to better illustrate the techniques of this invention will now be further illustrated by the following specific examples, but not limited to:

[0085] 实施例一:阿维菌素微囊悬浮剂的配方组分 Avermectin capsule suspension formulation ingredients: one case of [0085] Embodiment

Figure CN102100229AD00101

[0087] 将30kg的杀虫剂阿维菌素折百原药与3kg的载体白炭黑分散在15kg的大豆油中(市购)搅拌均勻(油相)后通过砂磨机砂磨,直到物料的平均粒度达到2um〜8um,然后加入4kg的甲苯二异氰酸酯TDI (沧州大化TDI有限责任公司)搅拌均勻(油相);然后配制水相:用10%聚乙烯醇PVA水溶液IOkg加入40kg的去离子水中搅勻(水相);把配制好的油相物料到入水相并开启高速均化,形成稳定的0/W乳液;开启搅拌(维持800转/min), 然后将均化好的乳液升温至70°C,维持稳定的囊壁材料固化温度3小时,后加入PH调节剂0. Ikg的冰醋酸调PH值至7左右、有机硅消泡剂0. 5kg搅拌均勻,即制得30%阿维菌素微囊悬浮剂100kg。 After [0087] The avermectin insecticides 30kg converted into 100% of the carrier 3kg silica dispersed in 15kg of soybean oil (commercially available) and mix (oil phase) sanding by a sand mill until the average particle size of the material reaches 2um~8um, then toluene diisocyanate TDI of 4kg (Changzhou Dahua TDI Co., Ltd.) and mix (oil phase); the aqueous phase is then prepared: 10% PVA aqueous solution of polyvinyl alcohol was added 40kg of IOkg homogenized in deionized water (aqueous phase); the material to the prepared oil phase into the water phase and for the high speed homogenizer to form a stable 0 / W emulsion; open stirred (800 rpm maintaining / min), and then homogenized good emulsion was warmed to 70 ° C, to maintain a stable wall material curing temperature for 3 hours. after addition of 0. Ikg PH adjusting agent in glacial acetic acid to adjust PH value of about 7, a silicone antifoaming agent 0. 5kg stir that prepared 30% avermectin microcapsule suspension 100kg.

[0088] 将制备好的30%阿维菌素微囊悬浮剂料浆16. 7kg与填料硅藻土60kg、硫酸铵20kg、润湿剂Morwet EFff 1.0kg(Morwet系列产品为阿克苏诺贝尔公司产品)、分散剂Morwet D-4255. 0kg、粘结剂羟乙基纤维素(HEC)O. 5kg、崩解剂硅酸镁铝2kg搅拌捏合均勻,本实施例通过挤压造粒中的框式挤压造粒,寄出的粒子外径Imm〜2mm,最后通过沸腾烘干、筛分,得到外观黄褐色、水分控制在2. 5%左右,含量5%阿维菌素微囊粒剂。 [0088] The prepared 30% avermectin microcapsule suspension with a filler slurry 16. 7kg celite 60kg, ammonium sulfate 20kg, wetting agent Morwet EFff 1.0kg (Morwet products of Akzo Nobel Products ), dispersant Morwet D-4255. 0kg, binder hydroxyethylcellulose (HEC) O. 5kg, disintegrants magnesium aluminum 2kg stirred uniformly kneaded, granulated by extrusion according to the present embodiment in box extrusion granulation, the outer diameter of the particles sent Imm~2mm, and finally by boiling dried, sieved to give a brown appearance, moisture control at about 2.5%, content of 5% abamectin encapsulated granules.

[0089] 实施例二、甲草胺微囊悬浮剂配方组分[0090] [0089] Example II alachlor capsule suspension formulation components [0090]

Figure CN102100229AD00111

[0091 ] 将20kg的除草剂甲草胺加热至熔融状态,加入2kg的多苯基多亚甲基多异氰酸酯PAPI (德国拜耳公司)与Ikg的二苯基甲烷二异氰酸酯MDI (烟台万华聚氨酯股份有限公司)搅拌均勻(油相);把0.2kg甲基纤维素CMC加入至50kg的去离子水中,搅拌均勻(水相)把配置好的油相物料到入水相中并开启高速均化,形成稳定的0/W乳液;开启搅拌(维持400转/min),然后将均化好的乳液升温至40°C,同时缓慢加入0. 5kg的乙二胺,维持稳定的囊壁材料固化温度20小时,后加入润湿剂NNO 3. Okg(上海天坛助剂厂)、分散剂木质素磺酸钠(俄罗斯产)5. 0kg、崩解剂改性淀粉1. 0kg、白炭黑17kg、PH调节剂0. 2kg的冰醋酸、有机硅消泡剂0. 4kg搅拌均勻,即制得20%甲草胺微囊悬浮剂。 [0091] The herbicide alachlor 20kg heated to a molten state, addition of 2kg of polyphenyl polymethylene the PAPI polyisocyanate (Bayer Corporation) with diphenylmethane diisocyanate in MDI Ikg (Yantai Wanhua Shares Co.) and mix (oil phase); the methyl cellulose 0.2kg CMC was added to 50kg of deionized water, stir (aqueous phase) the oil phase material configured to turn on high speed into the aqueous phase and homogenized to form stable 0 / W emulsion; open stirred (400 rpm maintaining / min), and then homogenized emulsions were heated to 40 ° C, while ethylenediamine was slowly added 0. 5kg maintain the stability of the wall material 20 curing temperature hours, after the addition of a wetting agent NNO 3. Okg (Shanghai Heaven additives plant), sodium lignin sulfonate dispersant (Russia yield) 5. 0kg, modified starch disintegrants 1. 0kg, silica 17kg, PH 0. 2kg of glacial acetic acid modifier, silicone defoamer 0. 4kg stir, i.e. to obtain a 20% microcapsule suspension of alachlor.

[0092] 请配合参阅图1,图1是本发明实施例中采用的喷雾干燥造粒的流程示意图。 [0092] Please referring to FIG. 1, FIG. 1 is a schematic flow diagram of a spray drying granulation employed in the embodiment of the present invention. 本实例中采用的喷雾干燥机为ZPG-150型喷雾干燥机(常州先锋干燥工程有限公司),包括通过管道顺序连接的:浆料储罐1、进料泵2、喷嘴3、雾化器4、干燥塔5、旋风分离器6、引风机7、水膜除尘器8,采用蒸汽换热器供热。 Spray dryer employed in this example is ZPG-150 type spray dryer (Changzhou Pioneer dried Engineering Limited), comprising sequentially connected by piping: a slurry tank 1, a feed pump 2, a nozzle 3, atomizer 4 drying tower 5, a cyclone 6, draft fan 7, 8 water film dust, steam heat exchanger. 在热空气进风口处设有进风温度计91,在出风口处设有出风温度计91。 A hot air inlet provided at the inlet thermometer 91, a thermometer 91 is provided with an air outlet at. 该ZPG-150型喷雾干燥机设备主要技术参数为:水分蒸发量50〜 100Kg/h ;塔径/塔高4M/9. 7M ;操作温度:进温50〜100/出温30〜70 ;雾化器LPG-150 ; 转速18000r. p. m ;盘径150mm ;蒸汽耗量约325〜375kg/h ;干燥系统形式:开式循环系统; 供料方式:高压泵稳定送料;热风接触方式:并流方式;雾化方式:离心式雾化。 The ZPG-150-type spray dryer apparatus main technical parameters: water evaporation 50~ 100Kg / h; column diameter / tower 4M / 9 7M; operating temperature: 50~100 inlet temperature / outlet temperature of 30~70; fog . gasifier LPG-150; speed 18000r p m; 150mm diameter disc; steam consumption about 325~375kg / h; drying system forms: open-cycle system; feeding mode: high-pressure feeding pump stability; hot-contact manner: and flow mode; atomization: centrifugal atomization.

[0093] 造粒时,将喷雾干燥机中热空气进风口温度控制在80°C,将20%甲草胺微囊悬浮剂倒入料浆储罐,通过进料泵泵入雾化器使料浆雾化,后在干燥塔内产生高速旋转,从雾化器喷嘴旋转喷出后形成球形雾滴。 [0093] granulation, the hot air spray drier inlet temperature was controlled at 80 ° C, 20% alachlor microcapsule suspension was poured into the slurry storage tank, by atomizing the feed pump allows atomizing the slurry, after the high-speed rotation is generated in the drying tower to form spherical droplets ejected from the rotating atomiser nozzle. 雾滴受热后表面水分迅速蒸发,形成多孔状固体颗粒,最终干燥后形成微囊颗粒剂。 After the rapid evaporation of water droplet heated surface to form a porous solid particle, after the final dried granules formed microcapsules. 最后得到外观咖啡色颗粒,水分控制在3%左右,含量约40%的甲草胺微囊颗粒剂50kg。 Finally obtained granules brown appearance, moisture control in about 3%, about 40% of the content of microencapsulated alachlor granules 50kg. [0094] 实施例三、28%的毒死蜱微囊悬浮剂 [0094] Third, 28% chlorpyrifos microcapsule suspension of Example

[0095] [0095]

Figure CN102100229AD00121

[0096] 将28kg的毒死蜱原药加热热溶状态,然后加入3. Okg的多苯基多亚甲基多异氰酸酯PAPI (德国拜耳公司)与1. Okg的甲苯二异氰酸酯TDI (沧州大化TDI有限责任公司)搅拌均勻为油相;将1. Okg的乳化剂NP-10 (南京太化有限公司)、5kg的粘结剂黄原胶(2% )水溶液加入57. 5kg的去离子水中搅勻为水相;把配置好的油相到入水相并开启高速均化,形成稳定的0/W乳液;开启搅拌(维持1000转/min),然后将均化好的乳液升温至60°C,同时缓慢加入0. 5kg的二乙烯三胺,维持稳定的囊壁材料固化温度8小时,后加入1. Okg的Ε0/Ρ0嵌段聚醚分散剂DP-30、润湿剂NNO 2kg (上海天坛助剂厂),防腐剂苯甲酸钠0. 05kg、有机硅消泡剂0. 2kg搅拌均勻,即制得28%的毒死蜱微囊悬浮剂。 [0096] The drug was heated Chlorpyrifos 28kg of hot melt state, followed by the addition of 3. Okg polyphenyl polymethylene the PAPI polyisocyanate (Bayer Corporation) with 1. Okg toluene diisocyanate TDI (TDI limited Changzhou Dahua Ltd.) and mix an oil phase; and 1. Okg emulsifier NP-10 (too Nanjing Chemical Co., Ltd.), 5kg binder xanthan gum (2%) aqueous solution of deionized water, stir 57. 5kg a water phase; the oil phase is configured to open into the water phase and high-speed homogenizer to form a stable 0 / W emulsion; open stirring (1000 rpm maintained / min), and then homogenized emulsions were warmed to 60 ° C, while slowly adding 0. 5kg of diethylene triamine, wall material to maintain a stable curing temperature for 8 hours. after the addition of 1. Okg Ε0 / Ρ0 block polyether dispersant DP-30, a wetting agent NNO 2kg (Shanghai Temple of Heaven additives plant), sodium benzoate 0. 05kg, silicone defoamer 0. 2kg stir, i.e. 28% chlorpyrifos was prepared microcapsule suspension.

[0097] 同样,采用ZPG-150喷雾干燥机造粒,将热空气进风口温度控制在70°C,将28%毒死蜱微囊悬浮剂倒入料浆储罐,通过进料泵泵入雾化器使料浆雾化,后在干燥塔内产生高速旋转,从雾化器喷嘴旋转喷出后形成球形雾滴。 [0097] Similarly, using the ZPG-150 spray granulation, hot air inlet temperature was controlled at 70 ° C, 28% chlorpyrifos microcapsule suspension was poured into the slurry storage tank, by atomizing the feed pump allows atomized slurry, the high-speed rotation is generated in the drying tower to form spherical droplets ejected from the nozzle after the rotation atomizer. 雾滴受热后表面水分迅速蒸发,形成多孔状固体颗粒,最终干燥后形成微囊颗粒剂。 After the rapid evaporation of water droplet heated surface to form a porous solid particle, after the final dried granules formed microcapsules. 最后得到外观黄褐色颗粒,水分控制在2. 5%左右,含量约72%的毒死蜱微囊颗粒剂40kg。 Finally obtained granules brown appearance, moisture control at about 2.5%, about 72%, by weight microcapsules of chlorpyrifos granules 40kg.

[0098] 本发明的产品主要技术指标如下表: [0098] The main technical indexes of the present invention is as follows:

[0099] [0099]

Figure CN102100229AD00122
Figure CN102100229AD00131

[0100] 本发明由于是先农药微胶囊化,然后再制成颗粒剂,因此具有以下优点: [0100] Since the present invention is to microencapsulated pesticide, and then into granules, and therefore has the following advantages:

[0101] 1、抑制了许多环境因素如光、热、空气、雨水、土壤、微生物和其它化学物质对农药活性成分的不利影响,降低了农药的挥发、分解、氧化、降解和流失的速率,从而增强了农药的稳定性,扩大了使用范围。 [0101] 1, inhibits many environmental factors such as light, heat, air, rain water, soil, adverse effects of microorganisms and other chemicals pesticide active ingredient, reducing volatilization of pesticides, decomposition, oxidation, the rate of degradation and loss, thereby enhancing the stability of pesticides, expanding the scope of use.

[0102] 2、微囊颗粒剂剂中有效成分含量一般在5%〜75%之间。 [0102] 2, microencapsulated granules agent is the active ingredient content is generally between 5% ~ 75%. 与乳油比较,有效成分集中在的囊心里。 Compared with the EC, the active ingredient concentrated in the heart sac. 由于使用后固体微粒的作用,附着力加强不易随溶剂挥发,也是防治效果提高的因素。 Due to solid particles after use, easy to strengthen the adhesion with the solvent volatilized, it is also a factor to improve the control effect.

[0103] 3、降低了原药的急性毒性,减少了对人畜的刺激性、对环境的污染和对农作物的药害,不论对人畜还是生态环境,都更为安全可靠。 [0103] 3, reducing the acute toxicity of the original drug, reducing irritating to humans and animals, environmental pollution and phytotoxicity to crops, both to humans and animals or the environment, are more secure and reliable.

[0104] 4、微胶囊化后有效成分通过囊壁材料的渗透率可人为控制,缓释速度可事先设计。 [0104] 4, the microencapsulated active ingredient through the wall material of the permeability can be artificially controlled, sustained release rate may be pre-designed. 由于囊皮的保护,有效成分降解速度减缓,农药持效期可延长3〜10倍。 Since the balloon skin protection, the active ingredient slows degradation, extended persistence pesticide 3~10 times. 持效期延长, 就可以提高防治效果,减少施药次数,降低农业成本。 Extended persistence, you can improve the control effect, reduce the spraying times, reduce agricultural costs.

[0105] 5、有效降低甲苯、二甲苯等有机溶剂,从而有效达到减少环境污染和降低有机溶剂的使用量。 [0105] 5, reduce toluene, xylene and other organic solvents, so as to achieve effective use of reducing environmental pollution and reduce the amount of organic solvent.

[0106] 6、贮存稳定性和物理化学稳定性好,颗粒的崩解速度快,使用效果好。 [0106] 6, good physical and chemical stability and storage stability, rapid disintegration velocity of the particles, good results.

[0107] 7、与可湿性粉剂和悬浮剂相比,有效成分含量高,产品相对密度大,体积小,便于包装、贮存和运输。 [0107] 7, as compared with the wettable powders and suspensions, high active ingredient content, high relative density, small size, ease of packaging, storage and transportation.

Claims (10)

  1. 1.农药微囊颗粒剂,其特征在于,主要含有以下重量百分比的成分:农药有效成分5〜75%;囊壁材料 1〜10% ;润湿剂 1〜3%;分散剂 3〜8%;辅助剂 0〜10%;载体填料 补足总重量百分比为100%。 1. microencapsulated pesticide granules, characterized in that the main component comprises the following percentages by weight: 5~75% pesticide active ingredient; wall material 1~10%; ~ 3% wetting agent; dispersing 3~8% ; adjuvants 0 ~ 10%; total weight percent of the carrier filler make up 100%.
  2. 2.根据权利要求1所述的农药微囊颗粒剂,其特征在于,所述的可适用于该法制备农药微囊颗粒剂的原药成分包括:氟氯氰菊酯、毒死蜱、高效氰氰菊酯、顺式氯氰菊酯、苯醚菊酯、除虫菊素、吡虫啉、人工合成的引诱剂、氰戊菊酯、马拉硫磷、杀螟硫磷、甲基对硫磷、 乙基对硫磷、毒死蜱、辛硫磷、阿维菌素、丙线磷、苯线磷、二嗪磷、丁硫克百威、硫丹、阿维菌素、杀扑磷、哒螨灵、阿维菌素、氟硅唑、丙环唑、腈菌唑、苯醚甲环唑、三唑酮、甲草胺、乙草胺、丁草胺、野麦畏、二甲戊灵、异恶草松、氟乐灵、仲丁灵。 Pesticide microcapsule according to claim 1 of the granule, characterized in that said pesticide can be applied to the microcapsules prepared by the original drug granule ingredients comprising: cyfluthrin, chlorpyrifos, efficient cyanuric cyhalothrin, cypermethrin, phenothrin, pyrethrin, imidacloprid, synthetic attractants, fenvalerate, malathion, fenitrothion, methyl parathion, ethyl parathion, chlorpyrifos, suberic parathion, abamectin, Ethoprophos, fenamiphos, diazinon, carbosulfan, endosulfan, abamectin, methidathion, pyridaben, avermectin, flusilazole , propiconazole, myclobutanil, difenoconazole cyproconazole, triadimefon, alachlor, acetochlor, butachlor, triallate, pendimethalin, clomazone, trifluralin, sec-butoxy spirit.
  3. 3.根据权利要求1所述的农药微囊颗粒剂,其特征在于,所述的囊壁材料为合成聚脲树脂高分子材料。 Pesticide microcapsule according to claim granule of claim 1, wherein said wall material is a polyurea synthetic resin polymer material.
  4. 4.根据权利要求1所述的农药微囊颗粒剂,其特征在于,所述的润湿剂选自十二烷基硫酸钠、壬基酚聚氧乙烯、烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物硫酸盐磷酸盐、苯乙烯苯酚甲醛树脂聚氧乙烯醚磷酸酯盐、苯乙烯基酚聚氧乙烯聚氧丙烯醚、烷基萘甲醛缩合物磺酸盐、烷基丁二酸酯磺酸盐、斯盘SPAN、土温TWEEN中的两种或者三种以上的组合使用。 Pesticide microcapsule according to claim 1 of the granule, characterized in that said wetting agent is selected from sodium lauryl sulphate, nonylphenol, alkylphenol formaldehyde condensate sulfates, alkylphenol ether sulfates phosphates formaldehyde condensates, phenol-formaldehyde resin, a styrene polyoxyethylene ether phosphate ester salts, polyoxyethylene styryl phenol polyoxypropylene ethers, alkyl naphthalene sulfonate formaldehyde condensate acid, alkyl succinic ester sulfonate, Span the SPAN, TWEEN two kinds of soil temperature, or use a combination of more than three.
  5. 5.根据权利要求1所述的农药微囊颗粒剂,其特征在于,所述的分散剂选自萘磺酸钠甲醛缩合物、三苯乙烯基酚聚氧乙烯醚类和衍生物酯类、脂肪醇聚氧乙烯醚类、烷基酚聚氧乙烯醚类、高分子EO-PO嵌段共聚物、木质素磺酸盐、烷基酚聚氧乙烯甲醛缩合物硫酸盐、 烷基酚聚氧乙烯醚甲醛缩合物硫酸盐磷酸盐、苯乙烯苯酚甲醛树脂聚氧乙烯醚磷酸酯盐、 苯乙烯基酚聚氧乙烯聚氧丙烯醚、烷基萘甲醛缩合物磺酸盐、高分子疏型的支装共聚物、聚合羧酸盐类中的两种或者三种以上的组合使用。 Pesticide microcapsule according to claim granule of claim 1, wherein said dispersant is selected from naphthalene sulfonate formaldehyde condensates, tristyrylphenol polyoxyethylene ethers and esters derivatives, polyoxyethylene fatty alcohol ethers, polyoxyethylene alkylphenol ethers, EO-PO block copolymer, polymer, lignin sulfonate, formaldehyde condensate of alkylphenol sulfates, alkylphenol vinyl ether sulfates phosphates formaldehyde condensates, phenol-formaldehyde resin, a styrene polyoxyethylene ether phosphate ester salts, polyoxyethylene styryl phenol polyoxypropylene ethers, alkyl naphthalene sulfonate formaldehyde condensate polymer type sparse copolymers sticks, carboxylates polymerizing two or three or more types in combination.
  6. 6.根据权利要求1所述的农药微囊颗粒剂,其特征在于,所述的载体填料选自包括改性水溶淀粉、纤维素醚及其衍生物、硅酸镁铝、高龄土、硅藻土、凹凸棒土、葡萄糖、轻质碳酸钙、白炭黑、无机盐中的一种。 Pesticide microcapsule according to claim granule of claim 1, wherein said carrier comprises a modified water-soluble filler is selected from starch, cellulose ethers and derivatives thereof, magnesium aluminum silicate, kaolin, diatomaceous earth, attapulgite, glucose, calcium carbonate, silica, an inorganic salt of one.
  7. 7.根据权利要求1所述的农药微囊颗粒剂,其特征在于,所述的辅助剂选自粘结剂、崩解剂、PH调节剂、杀菌防腐剂、消泡剂中的一种或几种的组合;其中:所述的粘结剂选用聚乙烯醇、明胶、阿拉伯胶、黄原胶、聚丙烯酸钠、海藻酸钠、淀粉、纤维素及其衍生物,优选纤维素及其纤维素衍生物的一种,其占总重量百分比的0. 1〜2% ;崩解剂选自于硅酸镁铝、聚乙二醇PEG、改性淀粉、无机盐、白碳黑、硅胶的一种,其占总重量百分比的2〜5% ;所述的PH酸碱调节剂为冰醋酸、盐酸、氨水、乙醇胺、三乙醇胺中的一种,其占总重量百分比的0.1〜2% ;所述的杀菌防腐剂为:山梨酸钾、苯甲酸钠、甲醛、异噻唑啉酮类中的一种,其占总重量百分比的0. 〜0. 5% ;所述消泡剂:天然油脂、聚醚类消泡剂、高碳醇、有机硅消泡剂的一种,其占总重量百分比的0. 1〜1. 5% The granule pesticide microcapsule according to claim 1, characterized in that said adjuvants are selected from binders, disintegrating agents, PH adjusting agent, antiseptic, antifoaming agent, one or several combinations thereof; wherein: said selected binder polyvinyl alcohol, gelatin, acacia gum, xanthan gum, sodium polyacrylate, sodium alginate, starch, cellulose and derivatives thereof, preferably cellulose fibers, and one kind of derivatives which total 0. 1 to 2% by weight; the disintegrant is selected from magnesium aluminum silicate, polyethylene glycol PEG, modified starch, inorganic salt, white carbon, silica gel one of which is 2 ~ 5% by weight of the total; the PH adjusting agent is glacial acetic acid, hydrochloric acid, ammonia, ethanolamine, triethanolamine one which 0.1~2% of the total weight percent; the antiseptic to: potassium sorbate, sodium benzoate, formaldehyde, isothiazole oxazoline for ketone in which 0.5 percent by weight of the total ~ 0 5%; anti-foaming agent: natural oils, polyether-based defoaming agent, higher alcohol, an organosilicon defoamer, 0.5 weight percent of its total 1~1. 5% ;
  8. 8.农药微囊颗粒剂的制备方法,其特征在于,按照权利要求1〜8所述的原料组分和比例,包括以下步骤:第一步,通过农药微囊化技术,采用界面聚合法制备得到农药微囊悬浮剂或者微囊粉体;第二步,通过喷雾干燥干燥制粒或者挤压制粒干燥,从而得到农药微囊颗粒剂。 8. The method of preparing microencapsulated pesticide granules, characterized in that the raw material components according to claims 1~8 and the ratio, comprising: a first step, by microencapsulation of pesticides, prepared by interfacial polymerization pesticide suspension or microcapsules to obtain microcapsule powder; a second step of drying by spray drying granulation or extrusion granulation and dried to obtain a microencapsulated pesticide granules.
  9. 9.根据权利要求8所述的农药微囊颗粒剂的制备方法,其特征在于,.1、首先制备农药微囊悬浮剂,包括以下步骤::.1-1、将原药加热熔融加入适量的油相成囊材料搅拌均勻得到油相;.1-2、在水中预先加入乳化剂、分散剂搅拌均勻,然后加入预先配置好的油相,高速均化形成稳定水包油乳液;.1-3、降低转速,加入囊壁材料单体多元胺或者多元醇水溶液参加界面聚合反应形成聚脲树脂囊壁材料,反应温度控制在20°C〜80°C内,保持2小时〜24小时,使囊壁材料固化成囊;.1-4、待成囊材料完全固化成囊后,加入PH酸碱调节剂,调节至所需PH值范围内,再加入适量分散剂、辅助剂,搅拌均勻即制成农药微囊悬浮剂;上述1-1〜1-4步骤中工艺过程均在常压状态下实施完成;.2、然后将农药微囊悬浮剂通过干燥造粒得到微囊颗粒剂,所述的干燥造粒通过挤压造粒法造 9. The method of claim 8 prepared granule pesticide microcapsule according to claim, characterized in that, .1, pesticide microcapsule suspension is first prepared, comprising the steps of ::. 1-1, adding an appropriate amount of the original drug is heated and melted oil complementary bladder material stir obtain an oil phase; .1-2, emulsifying in water in advance was added, stirred uniformly dispersing agent, then adding the oil phase pre-configured, high-speed homogenizer to form a stable oil in water emulsion; .1 -3, reduce speed, wall material added to the polyol or polyamine monomer aqueous participate interfacial polymerization polyurea resin wall forming material, the reaction temperature is controlled within 20 ° C~80 ° C, 2 hours ~ 24 hours, that the material is cured into the bladder wall; .1-4, to be fully cured bladder material into the capsule, pH adjusting agent added PH, PH adjusted to the desired value within the range, then add the appropriate amount of dispersant, adjuvants, stir i.e. made pesticide microcapsule suspension; 1-1~1-4 above-described process steps are carried out at normal pressure embodiment; .2, then dried granulated pesticide microcapsule suspension obtained microcapsule granules, the dried granules made by an extrusion granulation method 粒干燥得到微囊颗粒剂,所述的挤压造粒法包括以下步骤:.2-1、通过载体填料对微囊悬浮剂进行吸附;.2-2、然后加入包括润湿剂、分散剂、辅助剂,再挤压造粒;.2-3、最后通过沸腾干燥得到微囊粒剂。 Granulated and dried to obtain granules microcapsules, the extrusion granulation method comprising the steps of: .2-1, capsule suspensions by adsorption on a carrier filler; .2-2 then added include wetting agents, dispersing agents , adjuvants, and then extrusion granulation; .2-3, and finally dried by boiling to give encapsulated granules.
  10. 10.根据权利要求8所述的农药微囊颗粒剂的制备方法,其特征在于,.1、首先制备农药微囊悬浮剂,包括以下步骤::.1-1、将原药加热熔融加入适量的油相成囊材料搅拌均勻得到油相;.1-2、在水中预先加入乳化剂、分散剂搅拌均勻,然后加入预先配置好的油相,高速均化形成稳定水包油乳液;.1-3、降低转速,加入囊壁材料单体多元胺或者多元醇水溶液参加界面聚合反应形成聚脲树脂囊壁材料,反应温度控制在20°C〜80°C内,保持2小时〜24小时,使囊壁材料固化成囊;.1-4、待成囊材料完全固化成囊后,加入PH酸碱调节剂,调节至所需PH值范围内,再加入适量分散剂、辅助剂,搅拌均勻即制成农药微囊悬浮剂;上述1-1〜1-4步骤中工艺过程均在常压状态下实施完成;.2、然后将农药微囊悬浮剂通过干燥造粒得到微囊颗粒剂,所述的干燥造粒通过喷雾干燥法 10. The method of claim 8 prepared granule pesticide microcapsule according to claim, characterized in that, .1, pesticide microcapsule suspension is first prepared, comprising the steps of ::. 1-1, adding an appropriate amount of the original drug is heated and melted oil complementary bladder material stir obtain an oil phase; .1-2, emulsifying in water in advance was added, stirred uniformly dispersing agent, then adding the oil phase pre-configured, high-speed homogenizer to form a stable oil in water emulsion; .1 -3, reduce speed, wall material added to the polyol or polyamine monomer aqueous participate interfacial polymerization polyurea resin wall forming material, the reaction temperature is controlled within 20 ° C~80 ° C, 2 hours ~ 24 hours, that the material is cured into the bladder wall; .1-4, to be fully cured bladder material into the capsule, pH adjusting agent added PH, PH adjusted to the desired value within the range, then add the appropriate amount of dispersant, adjuvants, stir i.e. made pesticide microcapsule suspension; 1-1~1-4 above-described process steps are carried out at normal pressure embodiment; .2, then dried granulated pesticide microcapsule suspension obtained microcapsule granules, drying said granulated by a spray drying method 粒干燥得到微囊颗粒剂,所述的喷雾干燥法是指直接采用微囊悬浮剂料浆直接喷雾干燥制粒,最终得到微囊颗粒剂;包括以下步骤:.2-1、首先将预先制备的微囊悬浮剂与填料载体和包括分散剂、湿润剂、辅助剂一起搅拌均勻,调整其浓度和粘度,得到喷雾用的浆料;2-2、然后将浆料经喷嘴雾化成微小的液滴,射入喷雾容器内,热空气与喷射滴并流或逆流进入干燥器;2-3、干净的热空气与料浆在造粒设备内与物料混合并蒸发料浆中的水分,形成颗粒剂。 Granulated and dried to obtain granules microcapsules, the spray-drying method is a suspension of microcapsules directly from the spray drying slurry directly granulated, microencapsulated granules finally obtained; comprising the steps of: .2-1, is first prepared in advance the capsule suspension with the filler comprises a carrier and dispersing agents, wetting agents, adjuvants uniformly with stirring, to adjust the concentration and viscosity of the obtained slurry was spray; 2-2, and then the slurry is atomized into fine liquid nozzle droplets, enters the spray container, with a hot air current or countercurrent droplet jet into the dryer; 2-3, clean and hot air mixed with the slurry and evaporated and the material moisture content in the slurry in the granulation equipment, the particles are formed agents.
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