OA10681A - Microencapsulated insecticide preparations and a process for the preparation thereof - Google Patents

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

Microencapsulated insecticide préparationsand a process for the préparation thereof 010681

The invention relates to a microencapsulated insecticide préparationcontaming as active ingrédient isomers of Cypermetlirm of the formula Iin a pre-selected ratio, furtliermore to a fonnulated product c ont amen g themicroencapsulated préparation and to a process for the préparationthereof.

Cypermethrin is a molécule containing 3 asymmetry centres and soît is a mixture of 8 optical isomers. According to the nomenclatureestabhshed by Michael Elliott hereinafter we wilî charaeter.se theconfiguration of the chiral carbon atom signed vvith et, wrh R and Srespectively " Cis " and " trans " désignations are covering the stericarrangement of the substituents of the cyclopropan rmg. We set theconfiguration of the first carbon atom of the cyclopropan rmg in the formoi IR or IS. Accordingly the IReisS isomer corresponds to 2,2dimethvlR 2',2'- dichlorovinyl) - 1(R) -cis- cyclopropan-carbcxylic acid -ai S i - cyano-m-phenoxy-benzyl-ester.

Cypermethrin characterised by formula I. is a well knowr* insecticide(Pest.Man. X. Ed., 178, {1994}} which contains ail of the 8 possibleisomers of the molécule. Its effectiveness can be increased resp. renderedlù more sélective by omitting the inactive isomers. Alpha-, beta- zeta-(Pes·. Man. X. Ed., 179, 180, 181, (7997g), and theta-Cypermethrir.s(Himganan patent spécification No. 198 373) hâve been developed on thishasts. The enumerated products are the active ingrédients ofcommereially available préparations which contain the isomers below:

Alpha - Cypermethrin = IReisR/IScisR in a 1:1 ratio

Beta - Cypermethrin = IReisS/ΙScisR : IRtransS lStransRin a 1:1 = 4/6 ratio

Thêta - Cypermethrin = IRtransS/lStransR ma 1:1 ratio Zêta - Cypermethrin = IRcis-transS/IScis-transS, cis trans = 4/6 ratio.

In the course of applying the products it tumed out quickly that asignificant skin irritation occures caused mainly by the cis isomers.(Aldbridge WN An assessment of the toxicological properties ofpyrethroids and their neurotoxicity, In: Critical Reviews in Environmental 2 0 î 0 6 8 î

Control Vol. 22, Issue 2, pp 89-104 (1992;) Tins effect js the mostsignificant in the case of alpha- Cypermethrin and the weakes: a: theta-Cypennethrin On persons usina and contactmg \vi:h the productséruptions, allergie reactions of individually different strength wereobserved too, which in the more acute cases were acccmpamed withshock-like symptoms, e.g. fever, swelling of the cheeks. These symptomsoccurred more heavily at persons usina the producïs by occupationParticularlv longer exposition to e.g. pesticides in closed places resultedirritation symptoms of longer or shorter duration. Accordmg tobiological studios Cypermethrin and the analogue pyrethroids are netallergens as such but they are significantly increasing and sensinsmg theeffects of other allergens. These by-effects lirmt their usage resp. theiruse requires spécial care.

Another significant problem of the molécule is that because ofliaving a broad spectrum it is very effective agamst eold-bioe ded speciesand more or less independently frorn the mode of the application i: kilisuse fui créatures as bees, predatory insects, mites etc. too, therefore i:ssélective application in the form of conventional products can net besecured. (llill, R.; Effect on non-target organisais in terrestriai andaquatic environment, In: The Pyrethroid Insecticides. Ed. Leahey J.?., pp151 -262 i 1985) Taylor and Francis, London.).

The situation is further worsened by the sigmficant repelient i.e.frightening effect of the pyrethroids including Cypermethrin and sc theycan not be used directlv or only with little efneacy agamst hidir.g pesrs.

For securing safe handlmg of dangerous materials. e.g. powerfulpoisons, explosives procedures were developed in the last décades en thebasis of coîîoid Chemical results under the compréhensive name ofmicroencapsuiation (Bungenberg de Jong H D, In. Colloid Sci, Ed H.R.Rniyt; Elsevier, Amsterdam, Vol.2, p. 249- (194°): J.R Nixcn.ed.,Microencapsuiation, Marcel Dekker, Inc., New York (1976k T. Rondo,ed., Microencapsuiation, Techno Inc., Tokyo, Japan (1979V). The point ofthis is that on the surface of colloid size granules or droplets a new phaseis niade, quasi the substance is packed in, by which a substance with newcharacteristics is obtained. This process can be carried ont in liquid andin vapour phase , in solution or in melt, h can happen physically by phaseséparation (coacervation) resp. chemically by interfacial polymerizaîion.The fomied wrapping wall can be solid or semi-sohd. The size of the granule can van,- from 0,1 - 0,2 pm to the mm range, and us shape fromregular globe to an irregular form. The active ingrédient can be imbeddedinto the granule irregularly, ît can hâve matrix character. c: U can besurrounded regularly by the wrapping substance. These parametersdépend in a large measure from physico-chemical and coOoido-rheological characteristics of the System applied and wiüiin certainlunits, depending on the desired goal of the applied technique -technology. According to this microencapsulation is a general method,which should be specially studied and developed under the givenconditions. It is owing to this that microencapsulation procedures wereindividually developed for different active ingrédients , amcng them forinsecticides based first of ail on phosphate esters (Controlîed ReleasePesticides, ACS Symp. Sériés, No 53, .Am. Chem.Soc. Washington, D.C.,(1977)).

In the case of pyrethroids containing isomers which can îsomerize inthe presence of a base (e.g. β-Cypermethrin to o-Cypermetlmn HU210.098) microencapsulation may be a very difficult task. That can te thereason why no adéquate process has been worked ou: for such prcductsuntil now.

Our invention relates specially to microencapsulation of iscmermixtures of Cypermethrin having optimalized composition (first of ali betaand thêta Cypermethrins) and to the new products obtained this wav,winch can be used advantageously in the protection of plants, crops andtrees, m the veterinary therapeutics as ektoparasiticum, in the publichealth and in the extermination of "home pests" as mosquitoes, flies.cockroaches, ants, lice, fleas, ticks, ténuités etc. Although thedisadvantages and problems characteristic for Cypermethrin are knownlong ago and theoretically they could hâve been elimmated bymicroencapsulation, the development of products within the subject ofour invention has not been accomplished until the date of the présentapplication because of the individual character of microencapsulationwinch dépends on the active ingrédient. Microencapsulated productscontaining selected isomers of Cypermethrin were not known previov.sly.

In the products obtained by procedures according to our invention ailof the unfavourable features attnbutable to the contact activity ofCypermethrin isomers can be decreased or ceased by selecting iscmer 4 010681 mixtures (e.g. beta and thêta Cypermethrin) from the aspects of efnciencyand harmlessness. These aspects include but are not limited tto decreaseof toxicity exerted on warm- blooded and aquatic living créatures thelatter living in natural waters, reducing exposition and effects on humansdurmg usage, improvement of selectivity at plant protectmg applications,m as much as direct contact efficiency of the products witkin theprotection of our invention is limited to useful Articulata and they exertstomatotoxic effects only on pests feeding on treated planta They arefavourable from the aspect of developing résistance of pests, because byreducing the repellent effect of pyrethroids the uptake of léthal doses ismcreased. Because of controlled release of their active ingrédients theProducts according to the invention hâve an mcreased duration of acrivity,which is important fïrst of ail m professional extermination cf pesos andin public Health. The formulations according to our invention ccsplayfurther advantages in as much as they are water based versus theinflammable organic solvents used regularly in the formulation ofpyrethroids and characterised by high inhalation toxicity, or powders.

The wrappmg of the active ingrédient made it possible thaï a staffpreviously distinctlv sensitized to Cypermethrin can directly appîy thenew products. The acute toxicity measured on warm- blooded créaturesdecreased too: in the case of a microencapsulated product contaming25 % beta- Cypermethrin the acute per os LD50 value for rats was > 5000mg/kg while m the case of the control Chmmix 5SC (aqueous microsuspension containing 5% beta- Cypermethrin) the LD50 value was 1513.6 mg/kg. A significant advantage is that by the procedure according to ourinvention substances can be introduced application of which wasimpossible or cumbersome by the conventional methods. respecttvelytheir coexistence within a préparation was not solvable because of theirdifferent physical and Chemical indices. By this method attractants. fülingand activât}' enhancing materials, in particular cases further insecticidesand other auxihary substances can be applied according to choice. Byrepeatmg the microencapsulation procedure and by introduction of thesesubstances in the desired course a manifold microencapsulaticn ispossible. Tins way the active ingrédient can be coated with an extemalattractant envelope and products can be prepared which extennmate onlythe individuals of a given species or hiding pests. 5

Ci 0681 L/ι

Because the détergents used for forming colloïdal solution can bethe same as the surface active agents applied in the end produit themicroencapsulation procedure can be carried out also in a vvay, that theproduced microcapsule suspension should provide withcut isolation,preferably with further auxiliary materials the end producî.

In the course of developing our procedure one of our aims was toavoid the use of halogenated solvents and so without limiting dre scope10 of protection of our invention for these processes also alternativemethods applving ethvl acetate or petrol ether were worked out So alarge scale manufacture taking into account the protection cf theenvironment became possible.

On the base of the aboves our invention relates to u t uqi a microencapsulated insecticide préparation comprising as activeingrédient 0 001 - 80 vv % 1 RcisS/1ScisR and.er 1 Rtrar.sS T StransR.isomers or isomer mixtures of Cypermethrin of formula I. beside vvallmaterials optionally together vvith additional effect enhancing, attractant,filling and auxiliary materials or their mixtures wrapped or imbedded intosingle or manifold microcapsules of 1-2000 μτη size accordmg to figuresII. or III. optionally formulated to an insecticide product vvith additionalinsecticides and auxiliarv materials.

The microencapsulated préparation accordmg to the invention contrainsbeta or thêta Cypermethrin as active ingrédient; lignirg cellulosedérivatives, starch, gelatme, resin, polyamide, polyester, polycarbonate,polyuréthane, polyurea polymers as vvall material; insecticide synergents,preferably piperonylbutoxide or sesame oii as activity enhancer;pheromones and other attractants, various essential oils; sugars, four,bran, finely dispersed sawdust, pme-resin, guaiacol, ligniti and preferablyvvater or combinations of them; biologically and cherrdcally inertsubstances as filling materials e.g. finely dispersed cellulose, starch,limestone, silica gel povvder, silicic acid, paraffm oil or mixtures of them;emulgeating and suspending agents as auxiliary materials, e.g. ïomc ornon ionic tensides respectively stabilizers and/ or salts; pyrethroids e.g.tetramethrin, alletrin as additional insecticide and if destred furtherauxiliary materials.

Our invention relates furthermore to a process for preparing microencapsulated insecticide product characterised by formulatinglRcisS/1 ScisR and/or IRtransS/lStransR isomers or isomer mixtures ofCypermethrin of formula I. as active ingrédient vvith vvall materials, ifdesired vvith additional activity enhancing, attractant, filling and otherauxiliary' materials and if desired vvith additional insecticides tomicrocapsules of 1-2000 pm size accordmg to figures II. or IE. byapplying coacervation and/or interfacial polymerization method.

Aecording to the coacervation method of the invention the activeingrédient, activity enhancer, attractant, filling and auxiliary materialsfurthermore the vvall matenal are mixed vvith organic solvent, the mixtureis stirred vvith vvater if necessary in the présence of a detergent. the 0ÎC681 organic solvent is evaporated or precipitated by adding to i: addrtionalorganic or inorganie coagulant, or by adjusting the pH. the wali of triemicrocapsules obtained is formed to the desired strength by addmg *o it ifnecessary additional netting agents as formaldéhyde, glutaraldeh} de orpropylenoxide, then the suspension is filtered and dried or formulatedwithout filtration optionally by adding to it additional insecticides andauxiliary materials in the desired form, or the above processes arerepeated with the microcapsules containing suspension by adding to itadditional activity enhancers, attractants, fillmg and auxiliary maternais asdescribed above and from the manifold microencapsulated substance thedesired product is formulated as described above.

Accordmg to the interfacial polymerization method cf the inventionthe active ingrédient, activity enhancer, attractant, fillmg and auxiliarymaterials furthermore the wall material or a component o: the wallmaterial are mixed with organic solvent, the solution is dispersed m '.rateroptionally in the presence of a detergent, then on the surface of trieformed droplets polymerization or polycondenzation is mdticed by addingpolymerization initiating agent or bi or polyfunctional reagents, theformed wall is formed to the desired strength by adding to it if necessaryadditional netting agents as formaldéhyde, glutaralderiyde orpropylenoxide, then the suspension is filtered and dried or formulatedwithout filtration optionally by adding to it additional insecticides andauxiliary' materials m the desired form, or the above process is repeatedwith the microcapsules containing suspension by adding to it additionalactivity enhancers, attractants. fïlling and auxiliary' materials as describedabove and from the manifold microencapsulated substance the desiredproduct is formulated as described above.

Microencapsulation by coacervation and by interfacial polymerization canbe applied repeatedly, if necessary intermittentlv or combined.

Our invention relates furthermore to a process for the préparation ofinsecticide products characterised by that the microencapsulated productis formulated in the form of suspension concentrate, gel suspension,wettable powder dusting material, or as granules dispersible m water 8 010681

Suspension concentrâtes can be prepared by usine water. cispersingagent, preferably sodium-Iignin-sulfonate, wetting agent, préférablealkyl-aryl-polyglycolether and dialkyl-succinate sait, ar.tïge’atian agent,préférable propylenglycol and polysaccharide; gel suspensions by usingwater and dispersing agent, préférable ethoxylated-prepoxylated blockpolyiner and gelating agent, préférable polyacrylic acid a: pH — 6,5,wetiable powder products by using dispersing agent, préférable alkyl-aryl-10 naphthalene-sulfonic acid sodium sait, wetting agent, préférablepolyoxyetlivlen - alkyl ether, sliding agent and fïlling agent., préférablekaolin; dusting product by using sliding agent and fïlling agent.. préférabletalc and silicic acid. 15 Granules dispersible in water can be prepared front theniicroencapsuleted products accordmg to the invention by usuad wetgranulating and drying methods, préférable using as dispersing agentalkvl-aryl-sulfonic acid-sodium salt-formaldehyde condersare, as wettingagent dialkvl-sulfosuccinate and as binding - adhesive préférable 20 polyvinyl- pyrrolidone and lactose.

The scope of our invention is demonstrated by the exemples wrthoutlimiting it to them. 25

Examples: 1) 30 Into a 2 1 beaker supplied with mixer 1400 g distilled water and 1,5 g sodium-lauryl sulfate are added. The solution is mixed at 1222 r m. 60gbeta-Cypennetlirin and 30 g ethyl cellulose ("Hercules" N-202, 154 cP )are dissolved in 463 g of dichloromethane and this solution is poured tothe aqueous solution. The reaction mixture is stirred at room température 35 for 8 hours then the formed microcapsules are settled, decanted, washedwith water, filtered and dried under an infra lamp. The yield is 57.c?4 g;white powderlike product. Average size of the granules: 135 μη:, assay64 %. 2) 010681

It is proceed as in example 1) with the différence thaï instead cfdichloromethane 354 g chloroform are used. The yield is 57 g. whitepowderlike product. Average size of granules : 207 pm, assay 54.2 %. 3)

It is proceed as in exampîe 1) with the différence tha: instead c:dichloromethane 315 g ethyl acetate are used. The yield is 55.4 g. whitepowderlike product. Average size of granules : 241 pm, assay 06 %.Water content: 0.17 %. 4)

It is proceed as in example 1) with the différence thaï instead ofusing mira lamp the product is dried in open air. The yield is “5 g: whitepowderlike product. Average size of granules : 26" uni, assay 40 %.Water content: 34 %. 5)

It is proceed as in example 4) with the différence that as atîraetantadditive before microencapsulation 20 w % sugar is dissolved in distilledwater and the procedure is carried out with this solution. The yield is 77.2g; white powderlike product. Average size of granules : 254 μπ, assay 9.2 %. Sugar content : 7,7 %. Water content : 35.2 %. 6)

It is proceed as in example 1) with the différence tirât instead cf 60g, 50 g beta - Cypermethrin and as synergizmg agent 10 gpiperonylbutoxide ( PBO) are used. The yield is 56.2 g; white powderlikeproduct. Average size of granules : 237 pm, assay 45.3 %. PBO content:18%.

It is proceed as in example 6) with the différence that in place ofPBO sesame oil is used as synergizmg agent. The vield is 57 g. whitepowderlike product. Average size of granules : 75,6 pm. assay 4- %.Sesame oil content : 19 %. 10 Ü1068Î 8)

Into a I 1 beaker supplied with mixer 700 g. distilled water and 1.2 gsodium-lauril-sulfate are added. The solution is stirred at 1202 rm , 15 gthêta- Cypermethrin and 15 g. ethyl cellulose ( "Hercules" N-200. 154 cP) are dissolved in 175 ml dichloromethane and this solution ispoured to the aqueous one. The mixture is stirred for S heurs at roomtempérature then the forrned microcapsules are settled, decanted.washed with water, fîîtered and dried under mfra lamp. The yieîd is 27.4g; white powder. Average size of granules : 132 iim, assay 50.S %. 9)

It is proceed as in example 8) with the différence that mstead of15 g, 30 g ethylcellullose are used. The yield is 41 g; white powcerlikeproduct. Average size of granules: 239um, assay 32 %. 10.)

It is proceed as in example 8) with the différence that mstead of15 g, 25 g ethyl cellulose, mstead of 15g, 0,25 g theta-Cyperrnethrzi areused. The yield is 27.2 g; white powderlike product. Average size ofgranules : 118 μιη, assay 1 %. 11)

It is proceed as in example 8) with the différence that instead of15 g, 5 g thêta- Cypermethrin and as filling substance 10 g paraffïn cil areused. The yield is 26.2 g; white powderlike product. Average size ofgranules : 123 pm, assay 14,1 %. Paraffïn oil content : 31 %. 12)

Into a 250 ml beaker supplied with stirrer 2.5 g polyvmyl aloohol( PVA) (Merck, Mp ~ 72000 ), 57.5 g distilled water and 0.05 g soéium-lauryl-sulfate are added. The mixture is stirred at 1200 r min. 4 g beta-Cypermethrin are dissolved in 5.5 g xylene and tins solution is poured tothe aqueous one. The mixture is stirred for 10 minutes at roomtempérature then 36 ml 20 % sodium sulfate solution is dropped to it.After stirring for 15 minutes the pH is adjusted to 3,5 - 4 with citric acidthen the wall of the forrned microcapsules hardened by 2 mlformaldéhyde solution, for 1 more hour stirred, the product settled, 010681 decanted, washed with water, filtered and dried in air. The yield is S.2 g;white powder. Average size of granules: 243 gm, assav 42 %. 13.)

It is proceed as in example 12) with the différence that instead ofxylene 5.5 g aromatol are used. The yield is 8.7 g; white, powderhkeproduct. Average size of granules : 250 gm, assay 37.2 %.

It is proceed as in example 12) with the différence that instead ofpolyvinyl-alcohol (PVA) 2.5 g hydroxypropyl-methvl cellulose areused. The yield is 7.6 g; white powderhke product. Average size ofgranules : 217 gm, assay 33 %. 15)

It is proceed as in example 12) with the différence that instead ofpolyvinyl-alcohol 2.5 g of cellulose-acetate-phthalate are used. The yieldis 7.9 g; white powderhke product. Average size of granules : 203 gm,assay 37 %. 16)

Into an apparatus supplied with magnetic stirrer 60 g carbamide, 86 g formaldéhyde solution and 10 % aqueous ethanolamine solution areadded in a quantity that the pH of the formed mixture should be 7.5.Under stirring the mixture is warmed to 70°C and kept at this températurefor 2 hours. 9.5 g of the formed water-soluble carbamide- formaldéhydepolymer complex is dissolved in 160 g distilîed water, and 0.1 g Tween-20 detergent are added to it. While stirring at 1200 r/m 4 g beta-Cypermethrin dissolved in 5.5 ml xylene are added to it. After 10 minutesstirring the pH of the mixture is adjusted to 3,5-4 by addrng to it aqueouscitrie acid solution and then dropping to it 100 g sodium-sulfate in a 25 %solution. In order of strengthemng the walls of microcapsules 3 mlformaldéhyde solution are added to it then stirred for 1 hour. The productis decanted, washed with water, filtered and dried. The yield is 21g;white powderhke product. Assay : 17.2 %. Average size of granules : ! 68 gm.

Jh. 010681 17;

It is proceed as in example 16) with the différence thaï mslead offormaldéhyde 1 g gkitaraldehyde is used. The vield is 19.8 g: whitepowderlike product. Average size of granules: 16S pm, assay Z 6.95 :. IS;

Info a 100 ml beaker supplied with Turax mixer 40 g 0,5 c o PVAsolution and 4 g Dispergens A detergent are added. After stirring a: 3800r'm a solution of 4 g beta-Cypermethrin, 1,8 diphenyl-meftiane-diisocyanate solved in 8 g xvlol are added and stirred for additicnal 5minutes. Ίο the mixture a 40 % water solution of 1,4 g hexamethylene-diamine are added and it is stabilized with 1 g polyethyleneglycol aftersome minutes stirring. The pH of the mixture is adjusted to 5-5.5 by 33 %formic acid solution. The product is used directly. Average size ofgranules: 4.8 pm.

It is proceed as in example 18) with the différence that instezd ofdiphenyl-methane-isocyanate ONGRONAT CR 30-20 is used.

Average granule size: 8,0 pm. 20y

Info a 50 ml beaker supplied with Turax mixer 16.5 g disziied waterand 0.67 g MADEOL OR/95 BÂ detergent are added. After stirrmg at8000 r/ni the solution is cooled to 5°C. 4.26 g beta-Cypermethrin and1.03 g PAPI227 are dissolved in 8.51 g aromatol then this solution ispoured to the aqueous one. The mixture is stirred for 6 minutes then 1.43ml of 43.2% hexamethylene-diamine solution are dropped to it. .AfterstLrrmg for 3 more minutes the pH of the mixture is adjusted to 5-5.5 by33% formic acid solution. The product is used directly. Average size ofgranules : 1.4 pm.

It is proceed as in example 20) with the différence that instezd ofhexamethylene-diamine solution 1.03 ml 42 % aqueous diethylene-triamine solution are used. Average granule size : 4.4 pm. 13 22) 01 068 1

It is proceed as in example 20) with the différence thaï ir.sîead ofhexamethylene-diamine solution 2.06 ml of 11 % aqueeus 2,5-dimethyl- 2,5-hexanediol solution are used. Average size of granules 2.6 pm 23)

It îs proceed as in example 20) with the différence that instead ofhexamethylene-diamine solution 2.06 ml of 42.3 % aqueeus maîontc acidsolution are used. Average size of granules: 2.S uni. 24)

It is proceed as in example 20) with the différence that mstead ofhexamethylene-diamine solution 0.6 ml triethanolamine are used and0.75 g PBO synergetizing substance are added to the active ingrédient.Average size of granules: 2.3 pm. 23)

It is proceed as in example 20) with the différence that Atlox is usedas detergent. Average size of granules: 1.5 pm. 26)

Into a beaker supplied with Turax stirrer 25 ml 0.5 % PYA solutionand 0.1 g Wettol detergent are added. While stirring the solution at S000r/m the température is cooled to 5°C. 2 g beta-Cypermethrm and 2gsebacic acid chloride are dissolved m 3 g xylene then tins solution ispoured to the aqueous one. The mixture is stirred for 6 minutes then asolution prepared by dissolving 0.75 g ethylenediamine and 1.2 gdiethylenediamine in 10 ml water is dropped to it. The product whieh isused directly is stabilized at the end of the reaction by adding to it 5 ml25 % sodium sulfate solution.

Average size of granules: 5.7 pm. 2")

It is proceed as m example 22) with the différence that instead ofsebacic acid chloride 2 g of 2,4- toluene-diisocyanate and as detergent0.36 g MADEOL are used. Average size of granules : 4.6 pm. 14 28} 0 1 068 1

It is proceed as in example 22) with the différence that instead cf 5 xylene kerosene is nsed as solvent. Average size of granules: 3.5 pm 29;

Lnto a beaker suppliée! with stirrer 20 ml of distilled water, 0.4 gWettol are added then the solution is mixed at 1200 r/'min. 4 g ceta- 10 Cypermethrin and 0.4 g PAPI in 4 ml xylene are dissolvec. then thesolution is added to the aqueous one. After stirring for 15 minutes 2 ml42.3 % aqueous HMD A solution are added to it. It is stirred for 5 minutesthen the pH of the mixture is adjusted to 5-5,5 by a 33 % fermie acidsolution. The gained product is decanted, washed with water, fiitered and 15 dried. The yield is 4.2 g; white powderlike product. Assay: 44 %.Average size of granules: 67 pm. 30)

It is proceed as in example 29) with the différence that as the 20 aqueous phase 150 ml 0.5 % PVA solution and as the organic phase 6 gbeta-Cypermethrin and 6 g sebacic acid chloride dissclved in 3 S gdichloromethane are used. The wall of the capsules is developed byapplymg 6 ml 42.3 % HMDA solution. The yield is 14 g: white powder.Average size of granules : 73 pin. Assay: 31 %. 25 31)

It is proceed as in example 29) with the différence that 150 ml 0.5 %starch solution is used as proteetmg colloid. The yield is 12.7 g; whitepowder. Average size of granules: 85 pm. Assay: 29 %. 30 32) Préparation of gel

To 1500 g product prepared according to example 1) 1300 g waterand 100 g naphthalene sulfonic acid formaldéhyde sodium sait are addedafter 3 minutes stirring to the suspension 30 g propylenoxide-ethylenoxide 35 adduct (Phironic P65, BASF) were added. After stirring for 2 minutes 30g polvacrylic acid (Carbopol 940) are added to the mixture then the pH isadjusted to 6.5 by applying 1 N NaOH solution. 15 010681 Π

JJ ) Préparation of suspension concentrate (FW;

To 900 g product prepared according to example 8) 900 g water and38 g sodium lignin sulfonate are added under the mixing conditions olexample 30g

Then -15 g nonylphenol - polyglycolether ( EO = 10 ) -10 g dioctyl-sulfosuccinate sodium sait - 7 g propylenglycol and - 32 g 2% Xanthan gum aqueous solution are added successif ely, with 5minute stirring

Intensive stirring is continued for 5 mmutes after adding Xanthan gum. 34) Préparation of wettable powder product ( WP )

To 500 g capsules prepared according to example 16), while somngit continuously in a Lôdige mixer of 5 1 working volume 55 g ulkyl-naphthalene sulfonic acid sodium sait, 35 g polyoxyethylene alkyl ether, 15 g synthetic silicic acid ( Aerosil 300 ), and 395 g kaolin are addedsuccessively. Homogemzation is continued for 5 minutes. 35) Préparation of dustmg powder ( P)

To 500 g product prepared according to example 29) while stirrmg itcontinuously in a Lôdige mixer of 5 1 working volume 300 g talc, 2“5 gsilicic acid ( Wessalon ) and 25 g synthetic silicic acid (Aerosil 200 > areadded successively. Mixing is contmued for 5 minutes. 36) Préparation of water - dispersible granules (DG)

Into a Lôdige mixer of 5 1 working volume under continuonsstirring 850 g product prepared according to example 16) and then-85 g naphthalene sulfonic acid sodium sait formaldéhyde concentrate-15g dioctyl sulfosuccinate - 50 g polyvinyl-pyrrolidone( PVP K30) dissolved in 175 ml water - 50 g lactose are added successively. 15 mmutes after feeding the solution the stirring is stopped. The wetpowder mixture is formed to granules in a pan granulating equipmeut of550 mm diameter. The obtained product is dried in a vacuum drying ovenat 55 3C for approx. 2 hours to constant weight. 16 010681 37) Residual efficacy against house fly (Musca domestica)

Residual efficacy of the products prepared according to examples 33) and 34) on different surfaces and against home fly (Musca domesticaWHO/SRS) is demonstrated by the example below. The water dilutedproducts were sprayed to tiles and boards in the given doses with the helpof Potter spraying towers . The treated surfaces are kept in dark and at253C and 50-60 RH until using them. Tests were carried ouï in two 0 répétition using 10 -10 animais in each dose every time on surfacespreviously not used. The insects are exposed to the treated surfaces for30 minutes then placed into clean pétri dishes and fed with a foodconsisting water and sugar ad libitum. Mortality was evaluated after 24hours in the case of {lies and after 48 hours in the case of cockroaches. 5 The values were expressed as percent mortality.

The results show that the products prepared accordmg to exemples 33)and 34) gave 100'% efficiency for 15 weeks on both types of surfaces.Tlus is two times couger then the standard Coopex 25 WP (6 weeksï I» 010681

Residual efiiciencv of tested Products acainst home flies on tiles

Product active inured. treated surface "âge" in weeks dose ( mirm-l 0 0 k I 6 ! S 24 hour montants o ' o Su er 30 minute? cfewrssmpn Coopex 2 5 WP “ 100 100 100 1 100 I îoo ! 90 S5 Î4-y ; 15 i' 0 Exemple 33) 25 100 100 O O 100 100 loo Hoo : ioo ! r oo 100 Example 34) 25 100 100 O O 100 ! 100 100 h 0s ' 0 c-o I ’ 00 100 ’contains Permethrin as active ingrédient

Residual efhciencv of tested Products auainst home fîtes en board

Product active innred. trente d surface "ace" m week s 1 dose ( mfm-) | 0 1 ~r 6 Q O 10 il2 ; ' 12 5 24 hour monalmc % af 3 k minutes of expcsitic* Coopex 25WP* 100 100 100 100 85 7 > 35 1 15 2 5 15 ίο Example 33) 50 100 100 100 100 100 100 h 50 2 50 i ! 50' hco Example 34) 25 100 100 100 100 100 100 1 15 0 ' Y· 1 00 : ICO *contains Permethrin as active ingrédient

Residual efnciencv of tested Products acainst cochroaches (Blattelb uermamca on tues

Product active înured treated surface "ace" ir weeks dose ( ms/m-) 0 2 4 6 8 10 i 12 25 i 2 0’ 1 ->x 24 hour mortalitv % after 30 minutes of exposition Coopex 25WP* 200 100 100 100 100 100 75 I cOi h? U io Kordonl 0WP** 50 100 100 100 100 100 100 kâ 2 0 1 S 5 ! 401 Chinmix 5SC*** 25 100 100 100 100 100 îoo i ico : : oo h: i 65 Example 33) 25 100 100 100 100 100 îoo 1 îoo h oo h o o 200. contains Permethrin as active muredientcontains Cypermethrin as active ingrédientcontains Beta - Cypermethrin as active ingrédient

1S 010681

Residual efficiencv of tested products asainst cockroaches (Blattella cermarnca) on board

Product active intired treated surface "ace" in weeks dose (mu m-) 0 2 4 6 s 10 ! 12 i 15 i 20 125 24 hour mortalitv % after 30 minutes of expos .tion Coopex 25 WP’ 100 100 100 100 so 70 40 ΐ 20 h io io Kordon 10 WP’* 50 100 100 100 100 100 75 \ 50 I 65 i 25 i 5 Chinmix 5SC’** 25 100 100 100 100 100 100 G? 175 S 50 i 50 F.xample 33) 25 100 100 100 100 100 100 ! 100 î 100 : 100 ; 100 * contains Perinethnn as active ingrédient** contains Cypermethrin as active ingrédient*** contains Beta - Cypermethrin as active ingrédient ( 36) Residual efficacy agamst cockroaches (Blattella germanica )

Residual efficacy of the products prepared according to examples 33) and 34) îs demonstrated on different surfaces and agamst cockroaches (Blattella germanica) bv the example below.

Surfaces were treated as described m example 37). Products preparedaccording to examples 33) and 34) hâve shown a 100 % effectivenessthrough 25 weeks when applied at 25 mg/'m- dose on tiles and on board.

This is two times cuger then the efficiency of Coopex 25 V.7P at 200ing'm- dose and of Kordon 10 WP at 50 ing'm- dose (S and 4 resp. 10and 8 weeks).

Reagents applied: TWEEN 20- polyoxyethylene- 20- sorbitane - monolaurylate MADEOL AG/OR 95 - naphthalene - sulfonic acid PAPI 227 - polymethylene- polyphenylene- isocyanate

Atlox- polyoxyethylene- sorbitol- hexaoleate

Wettol - Phénol sulfonic acid - sodium sait HMDA - Hexamethylenediamine ONGROMAT CR 30-20 - polymethylene- polyphenyiene-isocyanate, 4,4-diphenyl-methane-diisocyanate (MDI)

Claims (17)

19 010681 Claims of the patent

1. A microencapsulated insecticide produc: ccmprasing as activeingrédient 0.001-80 w % 1 RcisS/1 ScisR and,or lRtransS/lSrransRisomers or isomer mixtures of Cypermethrin cf formula I beside wallmaterials optionally together with additional acttvity enhancing. attractant,filling and auxiliary materials or their mixtures wrapped or îmbedded intosingle or manifold microcapsules of 1 - 2000 pm size accordmg to figures II. or III. optionally formulated to an insecticide product with additionalinsecticides and auxiliary materials.

2. Microencapsulated product accordmg to clama 1. containing beta- orthêta- Cypermethrin as active ingrédient.

3. Microencapsulated product according to clama 1. containing as wallnaaterial of the microcapsules lignin, cellulose dérivatives, starch,gélatine, resin, polyamide, polyester, polycarbonate, polyuréthane, orpolyurea polymer.

4. Microencapsulated product according to clama 1. containing asactivity enhancer insecticide synergizing agent, preferably pipercnyl-butoxide or sesame oil.

5. Microencapsulated product accordmg to claim 1. containing asattractant pheromones, different odorants, sugars, flour, bran. fînelydispersed sawdust, pine resin, guaiacol, lignin and preferably water orcombinations of them.

6. Microencapsulated product accordmg to clama 1. containing asfilling material biologically and chemicallv inert substances, preferablyfînely dispersed cellulose, starch, limestone, silica powder, sih.cic acid,paraiün oil or mixtures of them.

7. Microencapsulated product accordmg to claim 1. contaming asauxiliary material emulsifying and suspending agents, preferably ionic ornon-ionic tensides, stabilizers and/or salts. 20 010681

8. Microencapsuleted product according to claim 1. containing asadditional insecticide tetramethrin or allethrin.

9. A process for the préparation of microencapsthated insecticideproducts which comprises fonnulating IRcisS IScisR and/or1 RtransS/1 StransR isomers or isomer mixtures of Cypermethrm offormula I. as active ingrédient with wall materials, and optionaJly withadditional activity enhancing, attractant, fïlling and other auxiliarymaterials and with additional insecticides to microcapsules of I- 20Ù0 pmsize according to figures II. or III. by applying a coacervation and/orinterfacial polymerization method.

10. A coacervation process according to claim 9. which comprisesmixing the active ingrédient, activity enhancer, attractant, Slltng andauxiliary materials,' and the wall material with organic solvent, rruxir.g themixture so obtained with water if destred in the presence of a detergent,evaporating the organic solvent or precipitating it by adding îo i:additional organic or inorganic coagulant, or by adjusting the pH, foraiingthe wall of the produced microcapsules to the desired strength by addingto it if desired additional netting agents as formaldéhyde, glutaraldehydeor propylenoxide, then filtering and drying the suspension or transformingit into the product without filtration optionally by adding to it additionalinsecticides and auxiliary' materials, or repeatmg the above process withthe microcapsule containing suspension by adding to it additional activityenhancers, attractants, fïlling and auxiliary materials and transforming themanifold microencapsulated substance to the product.

11. An interfacial polymerization process according to claim 9 whichcomprises mixing the active ingrédient, activity enhancer, attractant,fïlling and auxiliary materials and the wall material or a componen* ofwall material with organic solvent , dispersing the solution in water ifdesired in the presence of a detergent, then inducing polymerization onthe surface of the formed droplets by adding polymerization mitiatmgagent or bi or polyfunctional reagent, developing the fonned wa'î to thedesired strength by adding to it if desired additional netting agents asformaldéhyde, glutaraldehyde or propylenoxide, then filtering and diytngthe suspension or transforming it to the product without filtration 010681 optionally by adding to it additional insecticides and auxiliary materials,or repeating the above process with the microcapsule containingsuspension by adding to it additional activity enhancers, attrapants, fillingand auxiliary materials and transforming the manifold microencapsulatedsubstance to the product.

12. Process accorduig to claims 9.-11. which comprises repeatingcoacervation and interfacial- polymerization microencapsulation severaltimes, if desired intermittently or combined.

13. Process for the préparation of an insecticide product whichcomprises formulating the microencapsulated product of claim 1 assuspension concentrate, gel suspension, wettable powder product, dustingproduct, or water-dispersible granules.

14. Process according to claim 13. which comprises preparing thesuspension concentrate by using water; dispersing agent, preferablysodium lignin sulfonate; wetting agent preferably alkyl-aryl-polyglycolether, dialkyl-succinate sait; antigelmg agent, préférablepropylenglycol or polysaccharide.

15. Process according to claim 13. which comprises by preparing gelsuspension by using water; dispersing agent, preferably ethoxylated -propoxylated block polymer and gel forming agent, preferablypolyacrylic acid at pH = 6,5.

16. Process according to claim 13. which comprises preparing wettablepowder product by using dispersing agent, preferably alkyl-aryl-naphthalene-sulfonic acid- sodium sait; wetting agent, preferablypolvoxyethylene-alkyl ether; slidmg agent and filling substance,preferably kaolin.

17. Process according to claim 13. which comprises preparing dustingproduct by using sliding agent, filling substance, preferably talc andsilicic acid. Οί0681 1 S. Process according to daim 13. which comprises preparîng water-dispersible granules by using usual wet granulation and drying methods, 5 and as dispersing agent preferably alkyl-aryl-sulfonic acid- sodium sait-formaldehyde concentrate; as wetting agent dialkyl-sulfosuccinate and asbindmg agent and adliesive preferably polyvinyl- pyrrolidone and lactose.