CN1202802A - Microencapsulated insecticide and a process for preparation thereof - Google Patents
Microencapsulated insecticide and a process for preparation thereof Download PDFInfo
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- CN1202802A CN1202802A CN96198455A CN96198455A CN1202802A CN 1202802 A CN1202802 A CN 1202802A CN 96198455 A CN96198455 A CN 96198455A CN 96198455 A CN96198455 A CN 96198455A CN 1202802 A CN1202802 A CN 1202802A
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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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
Abstract
The invention relates to a microencapsulated insecticide product comprising as active ingredient 0.001-80 wt.% 1RcisS/1ScisR and/or 1RtransS/1StransR isomers or isomer mixtures of Cypermethrin of formula (I) beside wall materials optionally together with additional activity enhancing, attractant, filling and auxiliary materials or their mixtures wrapped or imbedded into single or manifold microcapsules of 1-2000 mu m size according to figures (II or III) optionally formulated to an insecticide product with additional insecticides and auxiliary materials.
Description
The present invention relates to a kind of insecticidal preparation of microencapsulation, this microencapsulation insecticide contains cypermethrin isomer active component shown in the structural formula I of predetermined ratio, and relates to product that contains this microencapsulation preparation and preparation method thereof.
Cypermethrin is the molecule that contains 3 asymmetric centers, so it is a kind of mixture that 8 kinds of optical isomers are arranged.Naming rule according to Michael Elliott foundation, we will describe the configuration of the asymmetric carbon atom of representing with α hereinafter respectively with R and S, come substituent spatial arrangements on the view cyclopropane ring with " cis (cis) " and " trans (trans) ".Our first ring carbon atom configuration of regulation cyclopropane is 1R or 1S.Therefore, the compound of the corresponding expression of 1RcsS isomer is 2,2 dimethyl-(2 ', 2 '-dichloroethylene)-1 (R)-cis-cyclopropane-carboxylic acid-α (S)-cyano group-m-phenoxy group-benzyl-ester.
Cypermethrin shown in the structural formula I is a kind of known insecticide that may contain 8 kinds of isomer molecules (Pest.Man. the 10th edition, 178 pages, (1994)).And when omitting nonactive isomer, it shows higher selectivity, and its validity strengthens.α-, β-, ζ-(Pest.Man. the 10th edition, 179,180,181 pages, (1994)) and θ-(Hungarian patent specification 198373) cypermethrin study on this basis.The product that can exemplify is that those can buy and contains following isomer as formulations of active ingredients:
α-cypermethrin=1RcisR/1ScisS, its content ratio is 1: 1;
β-cypermethrin=1RcisS/1ScisR: 1RtrahsS/1StrahsR, its content ratio is 1: 1
4: 6;
θ-cypermethrin=1RtransR/lStrahsS, its content ratio is 1: 1;
ζ-cypermethrin=1Rcis-trahsS/1Scis-trahsS, cis/trans
4/6;
Use in the process of these products, the tangible skin irritatin of the very fast appearance of meeting, stimulate and mainly cause (Albdridge W.N.:Anassessment ofthe toxicolgical properties of pyrethroids and theirneurotoxicity by the cis isomer, In:Critical Reviews in EnvironmentalControl the 22nd volume, the 21st phase, 89-104 page or leaf (1992)).This act on when using α-cypermethrin the most obvious and θ-cypermethrin is the slightest.Using and contacting the people that these products spray things, can also observe the individual allergy of the different orders of severity, than being attended by shock sample symptom, for example heating, facial swelling under the acute situations simultaneously.These symptoms are particularly serious in the full-time staff who uses these products.Particularly long-time, low coverage is liftoff is exposed to as insecticide following time, duration or length or short irritative symptoms may occur.According to biological study, cypermethrin and similar pyrethroid thereof are not anaphylactogen, but their can obviously increase the effect of other anaphylactogens or make other anaphylactogens responsive more.This side effects limit their application, when using them, need special prudent.
Another prominent question of this molecule is, because its broad spectrum disinfestation, it all has very strong effect to cold-blooded species, and irrespectively also beneficial organism is produced lethal effect more or less with occupation mode, for example honeybee, insect predator, acarid etc., therefore, the use selectivity when the existing product type of this insecticide is unsafe.(Hill，R.；Effect?on?non-target?organisms?in?terrestrial?and?aquaticenvironment，In：The?Pyre?throid?Insecticide，Ed.Leahey?J.P.，pp151-262(1985)Taylor?and?Francis，London.)。
The pyrethroid that comprises cypermethrin has significant anthelmintic action, promptly frightened worm effect, and this just makes situation more unfavorable, so they can not directly use or the insect of hiding is only produced very little effect.
For these dangerous substances are used in safety operation, for example potent poison developed a lot of methods in nearly ten years, these methods are to be colloidal chemistry achievement (the Bungenberg de Jong H D of microencapsulation based on the broad sense title, In Colloid Sci, Ed.H.R.Kruyt; Elsrvier, Amsterdam, Vol.2, p.249-(1949); J.R.Nixon, ed., Microencapsulation, Marcel Dekker, Inc., New York (1976); T.Kondo, ed., Microencapsulation, Techno Inc., Tokyo, Japan (1979)).The main idea of microencapsulation is: drip the new phase of surface formation at colloid sizing material particle or glue, half-formed material is encapsulated in wherein, obtains having the material of particular characteristics thus.No matter be in liquid phase or in gas phase, no matter be solution or at the molten state material, this method can both or be finished with the phase separation (cohesion) of physical property or with the interfacial polymerization of chemistry.The bag parietal layer that forms can be solid or semisolid.The scope of particle size is 0.1-0.2 μ m to the mm order of magnitude, and its shape can be regular spherical or irregular shape.Active component can embed in the spheroid brokenly and have medium characteristics, or is sealed regularly by bag wall material.These parameters are obtained from the big quantitative determination to the physicochemical characteristics of used system and colloid rheological properties, and depend on the intended purposes of the technology that is adopted under specific circumstances.Though this microencapsulation is a kind of conventional method, needs it is is distinguishingly researched and developed under different specified criterias.The method of microencapsulation will specifically be studied according to different active components, wherein for the research of insecticide at first based on phosphate (ControlledRelease Pesicides, ACS Symp.Series, No 53, Am.Chem.Soc.Washington, D.C., (1977)).
Isomerization (for example, β-cypermethrin is converted into α-cypermethrin (HU 210.098)) can take place in pyrethroid under the condition that alkali exists, but when pyrethroid contained isomer, the microencapsulation meeting was very difficult.Why Here it is does not also have enough ways to develop the reason of this series products so far.
Our invention has been particularly related to the method for the microencapsulation (first-selected β-and θ-cypermethrin) of the cypermethrin isomer mixture that contains the best group compound; and the new product that obtains in this way; these new products can advantageously be applied to the protection of plant, crop and trees; with the anti-external parasitic veterinary drug of conduct; also can be used for safeguarding public health and elimination " household insect ", for example insects such as mosquito, fly, cockroach, ant, louse, flea, tick, termite.Though, the shortcoming of cypermethrin and unfavorable characteristic are understood very early, and think in theory and can eliminate these defectives by microencapsulation, but, because microencapsulation can be had nothing in common with each other because of the difference of active component, thereby, the product development that can reach the object of the invention appears all failing to finish until the present invention.The microencapsulation product that contains cypermethrin selectivity isomer is that prior art never had.
In the product that makes by the method for the invention, the unfavorable factor of the contact action of all cypermethrin isomer all (for example is reduced or eliminates by the selection to isomer mixture, β-and θ-cypermethrin), select isomer mixture according to the factor of effect and avirulence aspect.These Considerations including, but not limited to: reduce the warm blooded animal and the hydrobiological toxic action of living, the latter lives in natural water area; Reduce contact and effect during use to the human body expose portion; Increase selectivity and reach the effect of protective plant; Equally, in protection domain of the present invention, product only produces directly contact (killing and wounding) effect to Articulata is biological, and only to the insect that has eaten the plant that crosses with this product treatment toxic action that opens.Product of the present invention helps improving the drug resistance of insect, and this is to make insect suck the insecticide of more lethal dose because this product can reduce the anthelmintic action of pyrethroid.Because product of the present invention can be controlled the release of active component, so its active duration increases, this advantage all is a primary importance in special insect is eradicated and in the public health.Preparation of the present invention has also shown other advantages, compares with pyrethroid ester formulation or inflammable organic solvent commonly used, and is that preparation of the present invention is based on water and have high toxicity on inhalation, or powder.
The sealing to make in the past of active component can directly be used this new product to the very sensitive staff of cypermethrin.Simultaneously, also can reduce hypertoxicity: with the LD of the Chinmix 5SC (the little aqueous suspension that contains 5% β-cypermethrin) of contrast to the homoiothermy biology
50Value 1513.6mg/kg compares, and the microencapsulation product that contains 25% β-cypermethrin is through the oral LD of rat
50Value＞5000mg/kg.
An obvious improvement is, in can being applied to putting into practice by the material of the method for the invention preparation and be impossible or pretty troublesome in previous methods, in the past unfavorable is because the material that coexists in the preparation does not hold them because of the difference of physics and chemical index each other mutually.According to the method, attractant, filler and active reinforcing agent, especially additional insecticide and other auxiliary substances can use on demand.Just can reach the multilayer microencapsulation by repeating the microencapsulation process and introducing above-mentioned substance in required step.Like this, active component is by outer attractant dressing and make product, and this product is only eliminated the individual biological or concealment insect of given category.
Because being used to form the washing agent of colloidal solution can be identical with the surfactant in the end-product, microencapsulation process so also can be finished by forming the non-isolated microcapsule suspension, and preferred end-product contains other auxiliary substances.
In the process of research the inventive method, our purpose is to avoid using halogenated solvent, and therefore, under the prerequisite that does not limit protection domain of the present invention, we have also studied the another kind of method that adopts ethyl acetate or benzinum.Like this, considering that environmental protection simultaneously, can realize large-scale production.The present invention relates to based on foregoing:
A kind of microencapsulation insecticidal preparation that contains 0.001-80 weight % active component, contained active component is 1RcisS/1ScisR and/or 1RtransS/1StransR cypermethrin isomer or the isomer mixture shown in structural formula I, except the cyst material that contains simultaneously, also can contain or not contain additional synergist, attractant, filler and auxiliary material or their mixture, these materials are sealed or are embedded in the single or multiple lift micro-capsule, this microcapsule structure is shown in accompanying drawing II or III, size is 1-2000 μ m, and this micro-capsule can also further be made pesticide product with additional insecticide and auxiliary material.
Microencapsulation preparation of the present invention contains: β-or θ-cypermethrin as active component; Lignin, cellulose derivatives, starch, gelatin, resin, polyamide, polyester, Merlon, polyurethane, polyurea polymer are as cyst material; The desinsection synergist, preferred piperonyl butoxide or sesame oil are as active reinforcing agent; Pheromones and other attractants; Various essential oils; The wood chip of sucrose, flour, bran chaff, fine gtinding, pine resin, guaiacol, lignin and suitable moisture content or their mixture; Employing has the material of biological and chemical inertia as packing material, for example fine cellulose, starch, lime stone, silica white, silicic acid, paraffin oil or their mixture; Emulsifier and suspending agent are for example distinguished ion or non-ionic surface active agent, stabilizing agent and/or salt as auxiliary material; As the pyrethroid of additional insecticide, for example tetramethrin, allethrin; And other auxiliary material of Cai Yonging as required.
Our invention also further relates to the preparation method of microencapsulation pesticide product, the characteristics of this method are: with the 1RcisS/1ScisR shown in the structural formula I and/or 1RtransS/1StransR cypermethrin isomer or isomer mixture as active component, make a kind of micro-capsule with cyst material, this micro-capsule also can contain the additional activity reinforcing agent as required, attractant, filler and other auxiliary material, also can contain additional insecticide if need, the micro-capsule size is 1-2000 μ m, structure is shown in accompanying drawing II or III, and reunion and/or interfacial polymerization method have been adopted in the preparation of micro-capsule.
Method of agglomeration of the present invention is that active component, active reinforcing agent, attractant, filler and auxiliary material are mixed in organic solvent with cyst material, if need in the presence of washing agent mixture be stirred with water; The organic solvent steaming is removed, or by coagulant that adds other organic or inorganic or the adjusting generation precipitation of passing through pH, can add the micro-capsule cyst wall that the agent (netting agents) of knotting obtains desirable strength by adding if desired, these agent of knotting for example are formaldehyde, glutaraldehyde or propylene oxide, then, with suspension filtered and dry or, make product to additional insecticide that wherein adds desired form and auxiliary material without filtration; Perhaps, the micro-capsule that will contain suspension carries out above-mentioned preparation process repeatedly, has added required additional activity reinforcing agent, attractant, filler and auxiliary material in the repetitive process, and multilayer microencapsulation material is made above-mentioned required product.
Interfacial polymerization method of the present invention is that a component with active component, active reinforcing agent, attractant, filler and auxiliary material and cyst material or cyst material is blended in the organic solvent, in the presence of being with or without washing agent solution is dispersed in the water; Then, by adding polymerization initiator or difunctional base or polyfunctional group base reagent in established drop surface initiated polymerization or polycondensation reaction, established cyst wall can add to add as required knots agent to obtain required cyst wall intensity, and the agent of knotting for example is formaldehyde, glutaraldehyde or propylene oxide; Then, with suspension filtered and dry or, can make required product without filtration by additional insecticide and the auxiliary material that add or do not add desired form; Perhaps, the micro-capsule that will contain suspension repeats above-mentioned preparation process, has added above-mentioned active reinforcing agent, attractant, filler and auxiliary material in the repetitive process, and multilayer microencapsulation material is made above-mentioned required product.
Reunite or the interfacial polymerization microencapsulation can be carried out repeatedly, also can be as needs with them alternately or in conjunction with carrying out.
Our invention has also related to the preparation method of pesticide product, and the characteristics of this method are: the microencapsulation product is made suspension-concentrates, gel suspension, wellability powder dusting material, maybe can be dispersed in particle in the water.
Can adopt water during the supending concentrate, dispersant, preferred dispersing agent is sodium-lignin-sulfonate; Size, preferred size is alkyl-aromatic radical-polyglycol ether and dialkyl group-succinate; Antigelling agent, preferred antigelling agent is propane diols and polysaccharose; Water and dispersant have been adopted in the preparation of gel suspension, and preferred dispersing agent is ethoxylation-propoxylation block polymer; Gelling agent, preferred pH are 6.5 polyacrylic acid; The wellability powder-product has adopted dispersant, preferred alkyl-aromatic radical-naphthyl-sulfonate sodium, size, preferred polyoxyethylene-alkyl ether; Slippage agent and filler, preferred kaolin; Slippage agent and filler have been adopted in the dusting product, preferably talc and silicic acid.
Make water-dispersible granule by the wet granulation and the drying means of microencapsulation product of the present invention by routine, preferred dispersing agent is alkyl-aromatic radical-sulfonic acid-sodium salt-formaldehyde condensation products; Dialkyl group-sulfosuccinate reaches preferably polyethylene pyrrolidones and lactose as bonding-adsorbent as size.
Scope of the present invention illustrates with the following example, but is not limited to this.Embodiment: 1)
1400g distilled water and the adding of 1.5g lauryl sodium sulfate are equipped with in the 2L beaker of agitator, this aqueous solution is to mix under 1200 rev/mins the condition at rotating speed, 60g β-cypermethrin and 30g ethyl cellulose (" Hercules " N-200,154cP) be dissolved in the 463g carrene, in the above-mentioned aqueous solution of this solution impouring.Reactant mixture at room temperature stirred 8 hours, subsequently, with established micro-capsule precipitation, the supernatant that inclines, wash with water, filtration and infrared lamp be dry down.Output is 57.64g; The white powder product.The mean size of particle is: 135 μ m, mensuration rate 64%.2)
Except embodiment 1 used carrene being used instead the replacement of 354g chloroform, identical with the method for embodiment 1, output is 57g; The white powder product.Mean particle size: 207 μ m, mensuration rate 54.2%.3)
Except embodiment 1 used carrene being used instead the replacement of 315g ethyl acetate, identical with the method for embodiment 1, output is 55.4g; The white powder product.Mean particle size: 241 μ m, mensuration rate 66%, water content: 0.17%.4)
Except adopting the infrared lamp desciccate to make into air drying among the embodiment 1, present embodiment is identical with the method for embodiment 1, and output is 75g; The white powder product.Mean particle size: 267 μ m, mensuration rate 54.2%.5)
Will be in distilled water and preparation carried out in this solution, present embodiment was identical with the method for embodiment 4 except before the microencapsulation of embodiment 4 as 20% (weight) sucrose dissolved of attractant additive.Output 77.2g, the white powder product.Mean particle size is: 254 μ m, and mensuration rate 9.2%, sugar content: 7.7%, water content: 35.2%.6)
Except embodiment 1 used 60g β-cypermethrin being made into use 50g β-cypermethrin and 10g piperonyl butoxide (PBO) replacement as synergist, present embodiment is identical with the method for embodiment 1.Output 56.2g, the white powder product.Mean particle size is: 237 μ m, mensuration rate 45.3%, PBO content: 18%.7)
Except the synergist PBO among the embodiment 6 is replaced to the sesame oil, present embodiment is identical with the method for embodiment 6.Output 57g, the white powder product.Mean particle size is: 75.6 μ m, mensuration rate 44%, sesame oil content: 19%.8)
700g distilled water and 1.2g lauryl sodium sulfate are joined in the 1L beaker that agitator is housed, and this aqueous solution is to stir under 1200 rev/mins the condition at rotating speed; (" Hercules " N-200 154cP) is dissolved in the 175g carrene, in the above-mentioned aqueous solution of this solution impouring for 15g θ-cypermethrin and 15g ethyl cellulose.Reactant mixture at room temperature stirred 8 hours, subsequently, with established micro-capsule precipitation, decant, wash with water, filtration and infrared lamp be dry down.Output is 27.4g; White powder.The mean size of particle is: 132 μ m, mensuration rate 50.8%.9)
Except the 15g ethyl cellulose among the embodiment 8 is made into the 30g ethyl cellulose, present embodiment is identical with the method for embodiment 8.Output 41g; The white powder product.Mean particle size: 239 μ m, mensuration rate 32%.10)
Except the 15g ethyl cellulose among the embodiment 8 being made into the ethyl cellulose of 25g, simultaneously used θ-cypermethrin is made into outside the 0.25g by 15g, present embodiment is identical with embodiment 8.Output 27.2g; The white powder product.Mean particle size: 118 μ m, mensuration rate 1%.11)
Except making the θ-cypermethrin among the embodiment 8 into 5g by 15g, and adopt the 10g paraffin oil as outside the filler, present embodiment is identical with the method for embodiment 8.Output 26.2g; The white powder product.Mean particle size: 123 μ m, mensuration rate 14.1%, paraffin oil content rate: 31%.12)
With 2.5g polyvinyl alcohol (PVA) (Merck, M
r≈ 72000) join in the 250ml beaker that has agitator, in this beaker, add 57.5g distilled water and 0.05g lauryl sodium sulfate.This mixture stirs under 1200 rev/mins speed conditions.4g β-cypermethrin is dissolved in the 5.5g dimethylbenzene, and with in the above-mentioned aqueous solution of this solution impouring.Mixture at room temperature stirred 10 minutes, and 20% metabisulfite solution with 36ml is added drop-wise to wherein then.Stir and with citric acid the pH value is transferred to 3.5-4 after 15 minutes, subsequently, established micro-capsule cyst wall is strengthened, stir again and make product precipitation, decant, washing, filtration after 1 hour and at air drying with 2ml formalin.Output 8.2g; White powder.Mean particle size: 243 μ m, mensuration rate 42%.13)
Except the dimethylbenzene among the embodiment 12 being used instead 5.5g aromatic alcohol (aromatol) replacement, present embodiment is identical with the method for embodiment 12.Output is 8.7g.The white powder product.Mean particle size: 250 μ m, mensuration rate 37.2%.14)
Except polyvinyl alcohol (PVA) among the embodiment 12 being used instead 2.5g hydroxypropyl-methylcellulose replacement, present embodiment is identical with the method for embodiment 12.Output is 7.6g.The white powder product.Mean particle size: 217 μ m, mensuration rate 33%.15)
Except the polyvinyl alcohol among the embodiment 2 being used instead 2.5g cellulose-acetic acid esters-phthalic acid ester replacement, present embodiment is identical with the method for embodiment 12.Output is 7.9g.The white powder product.Mean particle size: 203 μ m, mensuration rate 37%.16)
In the device of magnetic stirrer is housed, add 60g urea and 86g formalin, and add a certain amount of 10% monoethanolamine aqueous solution and make the pH value of mixture reach 7.5.Mixture is warming up to 70 ℃ when stirring, and under this temperature, kept 2 hours.The established water soluble urea of 9.5g-yuban compound is dissolved in the 160g distilled water, and adds the washing agent Tween-20 of 0.1g again.When stirring, the 5.5ml xylene solution of 4g β-cypermethrin is joined in the above-mentioned solution with 1200 rev/mins rotating speed.Stirred 10 minutes, and the pH value of mixture was transferred to 3.5-4, then to 25% the solution that wherein is added dropwise to 100g sodium sulphate with aqueous citric acid solution.For the curing microcapsules cyst wall, add 3ml formalin, stirred then 1 hour.With the product decant, wash with water, filter and dry.Output is 21g; The white powder product.Mensuration rate: 17.2%.Mean particle size: 168 μ m.17)
Except the formaldehyde among the embodiment 16 being used instead the replacement of 1g glutaraldehyde, present embodiment is identical with the method for embodiment 16.Output is 19.8g; The white powder product.Mean particle size: 168 μ m, mensuration rate 16.9%.18)
The 0.5%PVA solution and the 4g Dispergens A washing agent that in the 100ml beaker that the Turax blender is housed, add 40g.With 3800 rev/mins of stirrings of rotating speed, will contain 4g β-cypermethrin, the 1.8g diphenyl-methyl-vulcabond solution in 8g dimethylbenzene and add wherein, continue to stir 5 minutes.In mixture, add 40% aqueous solution contain the 1.4g hexamethylene diamine, after the stirred for several minute with the 1g polyethylene glycol with stabilized with mixtureization.The pH value of mixture transfers to 5-5.5 with 33% formic acid solution.Can directly use product.Mean particle size: 4.8 μ m.19)
Except the diphenyl-methyl among the embodiment 18-isocyanates being used instead ONGRONAT CR 30-20 replacement, present embodiment is identical with the method for embodiment 18.Mean particle size: 8.0 μ m.20)
In being housed, the 50ml beaker of Turax blender adds 16.5g distilled water and 0.67gMADEOL OR/95BA washing agent.Solution stirs under 8000 rev/mins rotating speed, is cooled to 5 ℃ subsequently.4.26g β-cypermethrin and 1.03g PAPI227 are dissolved in the aromatic alcohol (aromatol) of 8.51g, then, with the above-mentioned aqueous solution of this solution impouring.Mixture was stirred 6 minutes, in mixture, drip the hexamethylene diamine aqueous solution of 1.43ml 43.2% subsequently.The pH value of stirring back mixture more than 3 minutes transfers to 5-5.5 with 33% formic acid solution.Product can directly use.Mean particle size: 1.4g μ m.21)
Except the 42% diethylenetriamines aqueous solution of the hexamethylene diamine solution among the embodiment 20 being used instead 1.03ml replaced, present embodiment was identical with the method for embodiment 20, mean particle size: 4.4 μ m.22)
Except using the hexamethylene diamine solution among the embodiment 20 11%2 of 2.06ml instead, 5-dimethyl-2, outside the 5-hexylene glycol aqueous solution replaced, present embodiment was identical with the method for embodiment 20, mean particle size: 2.6 μ m.23)
Except the 42.3% malonic acid aqueous solution of the hexamethylene diamine solution among the embodiment 20 being used instead 2.06ml replaced, present embodiment was identical with the method for embodiment 20, mean particle size: 2.8 μ m.24)
Except the triethanolamine of the hexamethylene diamine solution among the embodiment 20 being used instead 0.6ml replaces, and add outside the 0.75gPBO synergist in active component, present embodiment is identical with the method for embodiment 20, mean particle size: 2.3 μ m.25)
Except using Atlox instead as the washing agent, present embodiment is identical with the method for embodiment 20, mean particle size: 1.5 μ m.26)
The 0.5%PVA solution and the 0.1g Wettol washing agent that in the beaker that the Turax agitator is housed, add 25ml.Solution is cooled to 5 ℃ with its temperature in 8000 rev/mins rotating speed stirring.2g β-cypermethrin and 2g decanedioic acid chlorine are dissolved in the 3g dimethylbenzene, then, with the above-mentioned aqueous solution of this solution impouring.Mixture continue to stir 6 minutes, subsequently, had dissolved the 0.75g ethylenediamine and the drips of solution of 1.2g diethylenediamine in 10ml water is added in the mixture with previously prepared.25% metabisulfite solution that adds 5ml when reaction finishes comes stable product, and this product can directly use.Mean particle size: 5.7 μ m.27)
Except using the decanedioic acid chlorine among the embodiment 22 1 of 2g instead, 4-toluene-two isocyanic acid replaces and uses 0.36g MADEOL instead as outside the washing agent, and present embodiment is identical with the method for embodiment 22, mean particle size: 4.6 μ m.28)
Replace as the solvent except the dimethylbenzene among the embodiment 22 being used instead kerosene, present embodiment is identical with the method for embodiment 22, mean particle size: 3.5 μ m.29)
In the beaker of agitator is housed, add 20ml distilled water and 0.4g Wettol, then the rotating speed of this solution with 1200 rev/mins stirred.4g β-cypermethrin and 0.4gPAPI are dissolved in the 4ml dimethylbenzene, this solution is joined in the above-mentioned aqueous solution.Stir after 15 minutes, in mixed liquor, add the 42.3%HMDA aqueous solution of 2ml.Continue to stir 5 minutes, and with 33% formic acid solution the pH value of mixture was transferred to 5-5.5 then.With products therefrom decant, washing, filtration and dry, output is 4.2g; The white powder product.Mensuration rate: 44%.Mean particle size: 67 μ m.30)
The 0.5%PVA solution that water among the embodiment 29 is changed into 150ml replaces, and organic facies replaces with the solution that 6g β-cypermethrin and 6g decanedioic acid chlorine are dissolved in the 38g carrene simultaneously, and capsule-wall forms with the HMDA solution of 6ml 42.3%.Step is identical with embodiment 29; Output is 14g, white powder.Mean particle size: 73 μ m.Mensuration rate: 31%.31)
Except 0.5% starch solution that adopts 150ml as the protective colloid, present embodiment is identical with the method for embodiment 29.Output 12.7g; White powder.Mean particle size: 85 μ m.Mensuration rate 29%.32) preparation of gel
In according to the 1500g product of embodiment 1 method preparation, add 1300g water and 100g naphthalenesulfonateformaldehyde formaldehyde sodium salt, stir in this suspension, add again after 3 minutes 30g propylene oxide-ethylene oxide adduct (Pluronic P65, BASF).Stir after 2 minutes, in mixture, add 30g polyacrylic acid (Carbopol 940), with .1N NaOH solution mixture pH value is transferred to 6.5g subsequently.33) preparation of suspension-concentrates (FW)
Under embodiment 30 described mixing conditions, in according to the 900g product of embodiment 8 methods preparation, add 900g water and 38g sodium lignin sulfonate.Then, general-15g nonyl phenol-polyglycol ether (EO=10)-10g dioctyl-sulfosuccinic acid sodium salt-7g propane diols and-the 32g 2% xanthan natural gum aqueous solution adds successively and all stirred 5 minutes at every turn, continues fully stirring 5 minutes when xanthan natural gum adds after.34) can soak into the preparation (WP) of powdered product
Under stirring condition, it is in 5 liters the Lodige blender, to wherein adding alkyl-naphthalene sulfonate salt, 35g polyoxyethylene alkyl ether, 15g synthetic silicic acid (Aerosil 300) and 395g kaolin successively that 500g is placed on actual volume according to the capsule of embodiment 16 preparation.Then homogenization is continued 5 minutes.35) preparation of dust formation powder (P)
Under stirring condition, be in 5 liter Lodige blender continuous stirring according to the product of embodiment 29 methods preparations at actual volume with 500g, to wherein adding 300g talcum, 275g silicic acid (Wessalon) and 25g synthetic silicic acid (Aerosil 200) successively.Continue to mix 5 minutes.36) preparation of water-particle dispersion (DG)
Continuous stirring 850g is by the product of embodiment 16 methods preparations in 5 liters Lodige blender, stops stirring after addings-85g naphthalene sulfonate salt formaldehyde condensation products-15g dioctyl sulfosuccinate-be dissolved in 50g polyvinylpyrrolidone (PVP K30) solution-50g lactose in the 175ml water is finished 15 minutes when feeding in raw material successively then.Is granulating in the cooking-pot type facility for granulating of 550mm with this wet powder mixture at diameter.Products obtained therefrom is dry in vacuum drying oven, and drying is to continue about 2 hours under 55 ℃ of conditions, to the product that obtains constant weight.37) to the residual effect of housefly (Musca housefly)
Products by embodiment 33 and 34 preparations will prove that they are in the different residual effect effects that are coated with on the face housefly (Musca housefly WHO/SRS) by following test example.Help by means of Potter spray tower is sprayed onto the product behind a certain amount of dilute with water on brick and tile and the plate face.Before use, these surface treated are kept under the condition of lucifuge, 25 ℃ and 50-60RH (relative moisture) always.Each dosage all carries out twice parallel test and selects 10 animals at every turn for use, and test is being carried out without the surface of using.These insects expose 30 minutes on surface treated, put into clean culture dish then, and use the random feeding of the food of being made up of water and sucrose.Through the death of 24 hours post-evaluation flies, rate is to estimate after 48 hours for cockroach.Evaluation of estimate is represented with the percentage lethality.
The result shows: will according to embodiment 33 and 34 the preparation products be coated on the two kinds of types surface, they in 15 weeks, all show 100% efficient.This result is that the nearly twice of marker Coopex 25 WP (6 week) is many.Be coated on product to be measured on the brick and tile to the residual effect effect of housefly
* contain permethrin and be coated on product to be measured on the plate face to the residual effect effect of housefly as active component
* contain permethrin and coat product to be measured on the brick and tile to the residual effect effect of cockroach (Blattella germanica) as active component
* containing permethrin contains cypermethrin as active component * * and contains the β cypermethrin as active component * * * and be coated on product to be measured on the plate face to the residual effect effect of cockroach (Blattella germania) as active component
* containing permethrin contains cypermethrin as active component * * and contains the β cypermethrin as active component 36 as active component * * *) to the residual effect of cockroach (Blattella germanica)
| Product | Active component | The number of weeks that treated surface is placed | |||||||||
| Dosage (mg/m 2) | 0 | 2 | 4 | 6 | 8 | 10 | 12 | 15 | 20 | 25 | |
| (on treatment surface) exposes lethality % in after 30 minutes 24 hours | |||||||||||
| ??Coopex ??25WP* | 100 | 100 | 100 | 100 | 100 | 90 | 85 | 40 | 15 | 0 | 0 |
| Embodiment 33 (product) | 25 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Embodiment 34 (product) | 25 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Product | Active component | The number of weeks that treated surface is placed | |||||||||
| Dosage (mg/m 2) | ?0 | ?2 | ?4 | ?6 | ?8 | ?10 | ?12 | ?15 | ?20 | ?25 | |
| (on treatment surface) exposes lethality % in after 30 minutes 24 hours | |||||||||||
| ?Coopex ?25WP* | ???100 | ?100 | ?100 | ?100 | ?85 | ?75 | ?35 | ?10 | ?10 | ?5 | ?0 |
| Embodiment 33 (product) | ???50 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| Embodiment 34 (product) | ???25 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| Product | Active component | The number of weeks that treated surface is placed | |||||||||
| Dosage (mg/m 2) | ??0 | ?2 | ?4 | ?6 | ?8 | ?10 | ?12 | ?15 | ?20 | ?25 | |
| (on treatment surface) exposes lethality % in after 30 minutes 24 hours | |||||||||||
| ??Coopex ??25WP* | ???200 | ?100 | ?100 | ?100 | ?100 | ?100 | ?75 | ?60 | ?30 | ?0 | ?0 |
| ??Kordon ??10WP** | ???50 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?95 | ?90 | ?85 | ?40 |
| ??Chinmix ??5SC*** | ???25 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?90 | ?65 |
| Embodiment 33 (product) | ???25 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| Product | Active component | The number of weeks that treated surface is placed | |||||||||
| Dosage (mg/m 2) | 0 | 2 | 4 | 6 | 8 | 10 | 12 | 15 | 20 | 25 | |
| (on treatment surface) exposes lethality % in after 30 minutes 24 hours | |||||||||||
| ??Coopex ??25WP* | 100 | 100 | 100 | 100 | 80 | 70 | 40 | 20 | 5 | 0 | 0 |
| ??Kordon ??10WP** | 50 | 100 | 100 | 100 | 100 | 100 | 75 | 50 | 65 | 25 | 5 |
| ??Chinmix ??5SC*** | 25 | 100 | 100 | 100 | 100 | 100 | 100 | 85 | 75 | 50 | 50 |
| Embodiment 33 (product) | 25 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Products by embodiment 33 and 34 preparations will prove that they are in the different residual effect effects that are coated with on the face cockroach (Blattella germanica) by following test example.Testing surface is all handled according to the method that embodiment 37 describes.The product that embodiment 33 and 34 is made is with 25mg/m
2Dosage be coated on brick and tile and the plate face, 25 the week in the efficient of them be 100%.This result is that Coopex 25 WP are at 200mg/m
2During dosage and Kordon 10WP at 50mg/m
2Efficient nearly twice many (being respectively 8 and 4 weeks, 10 and 8 weeks) during dosage.Agents useful for same: polysorbas20: polyoxyethylene-20-sorbitan-single dodecanoyl ester MADEOL AG/OR95: naphthyl-sulfonic acid PAPI 227: polymethylene-polyphenylene-isocyanates Atlox: polyoxyethylene-sorbierite-six oleate Wettol: phenolsulfonic acid-sodium salt HMDA: hexamethylene diamine ONGROMAT CR 30-20: polymethylene-polyphenylene-isocyanates, 4,3-diphenyl-methyl-vulcabond (MDI)
Claims (18)
1. microencapsulation desinsection product, this micro-capsule contains 0.001-80 weight % active component, contained active component is 1RcisS/1ScisR and/or 1RtransS/1StransR cypermethrin isomer or the isomer mixture shown in structural formula I, except containing cyst material, can also contain or not contain additional synergist, attractant, filler and auxiliary material or their mixture, these materials are sealed or are embedded in the single or multiple lift micro-capsule, this microcapsule structure is shown in accompanying drawing II or III, size is 1-2000 μ m, and these micro-capsules can also further be made pesticide product with additional insecticide and auxiliary material.
2. microencapsulation product according to claim 1, the active component that wherein contains are β-or θ-cypermethrins.
3. microencapsulation product according to claim 1 wherein contains lignin, cellulose derivatives, starch, gel, resin, polyamide, polyester, Merlon, polyurethane, polyurea polymer as cyst material.
4. microencapsulation product according to claim 1 wherein contains the desinsection synergist as active reinforcing agent, preferred piperonyl butoxide or sesame oil.
5. microencapsulation product according to claim 1 wherein contains the wood chip, pine resin, guaiacol, lignin of pheromones, different odorant agent, sucrose, flour, bran chaff, fine gtinding and suitable moisture content or their mixture as attractant.
6. microencapsulation product according to claim 1 wherein contains the biological and chemical inert substance as filler, preferred fine cellulose, starch, lime stone, silica white, silicic acid, paraffin oil or their mixture.
7. microencapsulation product according to claim 1 wherein contains emulsifier or suspending agent as auxiliary material, preferred ion or non-ionic surface active agent, stabilizing agent and/or salt.
8. microencapsulation product according to claim 1 wherein contains tetramethrin, allethrin as additional insecticide.
9. the preparation method of a microencapsulation pesticide product, this method comprises: with the 1RcisS/1ScisR shown in the structural formula I and/or 1RtransS/1StransR cypermethrin isomer or isomer mixture as active component, make a kind of micro-capsule with cyst material, this micro-capsule also can contain additional activity reinforcing agent, attractant, filler and other auxiliary material as required, also can contain additional insecticide, the micro-capsule size is 1-2000 μ m, structure is shown in accompanying drawing II or III, and the method for reunion and/or interfacial polymerization has been adopted in the preparation of micro-capsule.
10. method of agglomeration according to claim 9, this method comprises: active component, active reinforcing agent, attractant, filler and auxiliary material are mixed with cyst material and organic solvent, if need, in the presence of washing agent, mixture and water be mixed together; The organic solvent steaming is removed, or add the coagulant of other organic or inorganic, or the adjusting by pH makes it to produce precipitation, add the micro-capsule cyst wall that the agent of knotting obtains desirable strength by adding if desired, these agent of knotting for example are formaldehyde, glutaraldehyde or propylene oxide, then, with suspension filtered and dry or, in required product, add or do not add additional insecticide and auxiliary material make product without filtration; Perhaps, the micro-capsule that will contain suspension repeats above-mentioned preparation process, adds required additional activity reinforcing agent, attractant, filler and auxiliary material in the repetitive process, and multilayer microencapsulation material is made product.
11. interfacial polymerization method according to claim 9, this method comprises: the component of active component, active reinforcing agent, attractant, filler and auxiliary material and cyst material or cyst material is blended in the organic solvent, if need in the presence of washing agent, solution be dispersed in the water; Then, by adding polymerization initiator or difunctional base or polyfunctional group base reagent at established drop surface initiated polymerization, add the additional agent of knotting as required and make established cyst wall reach desirable strength, the agent of knotting for example is formaldehyde, glutaraldehyde or propylene oxide; Then, with suspension filtered and drying, or in product, add or do not add additional insecticide and auxiliary material and make product without filtering; Perhaps, the micro-capsule that will contain suspension repeats above-mentioned preparation process, adds active reinforcing agent, attractant, filler and auxiliary material in the repetitive process, and multilayer microencapsulation material is made product.
12. according to the described method of claim 9-11, comprising will reunite and the interface-the polymerization microencapsulation repeats for several times, if need them to replace or in conjunction with carrying out.
13. the preparation method of a pesticide product, this method comprises: form microencapsulation product as claimed in claim 1, this product is suspension-concentrates, gel suspension, wellability powder-product, dusting product, maybe can be dispersed in particle in the water.
14. according to the method for claim 13, comprising: the supending concentrate, can adopt water; Dispersant, preferred sodium lignin sulfonate; Wellability reagent, preferred alkyl-aromatic radical-polyglycol ether, dialkyl group-succinate; Antigelling agent, preferred propane diols or polysaccharide.
15. method according to claim 13, comprising: preparation gel suspension, can adopt water; Dispersant, preferred ethoxylation-propoxylation block copolymer; With gel shaped dose, preferred pH value is 6.5 polyacrylic acid.
16. method according to claim 13, comprising: preparation is soaked into. and the property powdered product, can adopt dispersant, preferred alkyl-aromatic radical-naphthyl-sulfonate sodium; Size, preferred polyoxyethylene-alkyl ether; Slippage agent and filler, preferred kaolin.
17. method according to claim 13, comprising: the preparation dusting powder, can adopt slippage agent, filler, preferably talc and silicic acid.
18. method according to claim 13, comprising: the preparation water-dispersible granule, can adopt conventional wet granulation and drying means, and preferred alkyl-aromatic radical-sulfonic acid-sodium salt-formaldehyde condensation products is as dispersant; Dialkyl group-sulfosuccinic acid reaches preferably polyethylene pyrrolidones and lactose as adhesive and adsorbent as wetting agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUP9503021 | 1995-10-20 | ||
| HU9503021A HU215572B (en) | 1995-10-20 | 1995-10-20 | Encapsulated insecticidal compositions and method for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1202802A true CN1202802A (en) | 1998-12-23 |
Family
ID=10987304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96198455A Pending CN1202802A (en) | 1995-10-20 | 1996-10-16 | Microencapsulated insecticide and a process for preparation thereof |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPH11514360A (en) |
| KR (1) | KR19990066935A (en) |
| CN (1) | CN1202802A (en) |
| AP (1) | AP9801224A0 (en) |
| AR (1) | AR008984A1 (en) |
| AU (1) | AU7326196A (en) |
| BG (1) | BG102463A (en) |
| BR (1) | BR9611016A (en) |
| CZ (1) | CZ118298A3 (en) |
| EA (1) | EA199800390A1 (en) |
| EE (1) | EE9800119A (en) |
| HR (1) | HRP960472A2 (en) |
| HU (1) | HU215572B (en) |
| IS (1) | IS4717A (en) |
| NO (1) | NO981747L (en) |
| OA (1) | OA10681A (en) |
| PL (1) | PL326504A1 (en) |
| SK (1) | SK49398A3 (en) |
| TR (1) | TR199800728T2 (en) |
| WO (1) | WO1997014308A1 (en) |
| YU (1) | YU56096A (en) |
| ZA (1) | ZA968803B (en) |
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| CN1095738C (en) * | 1998-03-27 | 2002-12-11 | 标准模具有限公司 | Cylindrical main-tube insertion piece for injection moulding and mfg. method therefor |
| CN100413576C (en) * | 2003-05-11 | 2008-08-27 | 内盖夫研发局属本古里昂大学 | Encapsulated essential oils |
| CN101132851B (en) * | 2005-03-01 | 2010-11-24 | 巴斯福股份公司 | Fast-release microcapsule products |
| CN102387819A (en) * | 2009-04-06 | 2012-03-21 | 柳韩-金伯利有限公司 | Absorbent article comprising an encapsulated plant extract exhibiting an insecticidal effect |
| CN101163401B (en) * | 2005-04-22 | 2012-07-04 | 恩德拉（共同）股份公司 | Innovative formulation |
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| JP4794120B2 (en) * | 2003-08-20 | 2011-10-19 | 住化エンビロサイエンス株式会社 | Microencapsulated composition |
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| ITMI20050730A1 (en) * | 2005-04-22 | 2006-10-23 | Chemia S P A | PREPARATION OF COMPOSITIONS WITH HIGH ACTIVITY INSECTICIDE |
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| US4670246A (en) * | 1984-11-05 | 1987-06-02 | Pennwalt Corporation | Microencapsulated pyrethroids |
| SE468740B (en) * | 1986-03-17 | 1993-03-15 | Sumitomo Chemical Co | MICROINCAPTED INSECTICID AND / OR ACARICID PYRETROID COMPOSITION, SET TO REGULATE INSECTS AND / OR ANIMALS THEREOF AND PROCEDURES FOR PREPARING THEREOF |
| JP2676082B2 (en) * | 1987-12-25 | 1997-11-12 | 住友化学工業株式会社 | Microcapsules for cockroach control |
-
1995
- 1995-10-20 HU HU9503021A patent/HU215572B/en not_active IP Right Cessation
-
1996
- 1996-10-16 SK SK493-98A patent/SK49398A3/en unknown
- 1996-10-16 CN CN96198455A patent/CN1202802A/en active Pending
- 1996-10-16 EE EE9800119A patent/EE9800119A/en unknown
- 1996-10-16 CZ CZ981182A patent/CZ118298A3/en unknown
- 1996-10-16 BR BR9611016A patent/BR9611016A/en not_active Application Discontinuation
- 1996-10-16 EA EA199800390A patent/EA199800390A1/en unknown
- 1996-10-16 PL PL96326504A patent/PL326504A1/en unknown
- 1996-10-16 TR TR1998/00728T patent/TR199800728T2/en unknown
- 1996-10-16 JP JP9515639A patent/JPH11514360A/en not_active Ceased
- 1996-10-16 AP APAP/P/1998/001224A patent/AP9801224A0/en unknown
- 1996-10-16 KR KR1019980702856A patent/KR19990066935A/en not_active Application Discontinuation
- 1996-10-16 WO PCT/HU1996/000060 patent/WO1997014308A1/en not_active Application Discontinuation
- 1996-10-16 AU AU73261/96A patent/AU7326196A/en not_active Abandoned
- 1996-10-17 HR HRP9503021A patent/HRP960472A2/en not_active Application Discontinuation
- 1996-10-18 YU YU56096A patent/YU56096A/en unknown
- 1996-10-18 ZA ZA968803A patent/ZA968803B/en unknown
- 1996-10-21 AR ARP960104826A patent/AR008984A1/en unknown
-
1998
- 1998-04-16 IS IS4717A patent/IS4717A/en unknown
- 1998-04-17 NO NO981747A patent/NO981747L/en unknown
- 1998-04-17 OA OA9800045A patent/OA10681A/en unknown
- 1998-05-19 BG BG102463A patent/BG102463A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095738C (en) * | 1998-03-27 | 2002-12-11 | 标准模具有限公司 | Cylindrical main-tube insertion piece for injection moulding and mfg. method therefor |
| CN100413576C (en) * | 2003-05-11 | 2008-08-27 | 内盖夫研发局属本古里昂大学 | Encapsulated essential oils |
| CN101132851B (en) * | 2005-03-01 | 2010-11-24 | 巴斯福股份公司 | Fast-release microcapsule products |
| CN101163401B (en) * | 2005-04-22 | 2012-07-04 | 恩德拉（共同）股份公司 | Innovative formulation |
| CN102387819B (en) * | 2009-04-06 | 2015-02-18 | 柳韩-金伯利有限公司 | Absorbent article comprising an encapsulated plant extract exhibiting an insecticidal effect |
| CN102387819A (en) * | 2009-04-06 | 2012-03-21 | 柳韩-金伯利有限公司 | Absorbent article comprising an encapsulated plant extract exhibiting an insecticidal effect |
| CN103907645A (en) * | 2013-04-26 | 2014-07-09 | 华南农业大学 | Periplaneta australaslae attractant |
| CN103918646B (en) * | 2014-04-22 | 2016-02-24 | 福建农林大学 | A kind of Synergistic type pleocidin microballoon suspending agent and preparation method thereof |
| CN103918646A (en) * | 2014-04-22 | 2014-07-16 | 福建农林大学 | Synergystic pleocidin microsphere suspending agent and preparation method thereof |
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| CN105961383B (en) * | 2016-05-19 | 2019-01-01 | 重庆中邦药业（集团）有限公司 | A kind of longicorn lures the preparation method of contact insecticide |
| CN106614564A (en) * | 2016-09-30 | 2017-05-10 | 扬州大学 | Hygienic insecticide microcapsules and preparation method thereof |
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| CN110869406A (en) * | 2017-07-31 | 2020-03-06 | 陶氏环球技术有限责任公司 | Additive composition and method |
| CN114246182A (en) * | 2021-12-30 | 2022-03-29 | 江苏仁信作物保护技术有限公司 | Pendimethalin microcapsule suspending agent and production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HU9503021D0 (en) | 1995-12-28 |
| AU7326196A (en) | 1997-05-07 |
| AP9801224A0 (en) | 1998-06-30 |
| SK49398A3 (en) | 1998-09-09 |
| JPH11514360A (en) | 1999-12-07 |
| YU56096A (en) | 1998-11-05 |
| TR199800728T2 (en) | 1998-08-21 |
| HRP960472A2 (en) | 1998-02-28 |
| IS4717A (en) | 1998-04-16 |
| CZ118298A3 (en) | 1998-09-16 |
| OA10681A (en) | 2001-05-03 |
| AR008984A1 (en) | 2000-03-08 |
| NO981747L (en) | 1998-06-19 |
| NO981747D0 (en) | 1998-04-17 |
| ZA968803B (en) | 1997-05-27 |
| KR19990066935A (en) | 1999-08-16 |
| HUT76140A (en) | 1997-07-28 |
| EA199800390A1 (en) | 1998-12-24 |
| HU215572B (en) | 1999-01-28 |
| WO1997014308A1 (en) | 1997-04-24 |
| BG102463A (en) | 1999-04-30 |
| PL326504A1 (en) | 1998-09-28 |
| EE9800119A (en) | 1998-10-15 |
| BR9611016A (en) | 1999-07-13 |
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