CA2235280A1

CA2235280A1 - Microencapsulated insecticide preparations and a process for the preparation thereof

Info

Publication number: CA2235280A1
Application number: CA 2235280
Authority: CA
Inventors: Ildiko Bakonyvari; Agnes Janosi; Laszlo Csiz; Laszlo Pap; Istvan Szekely; Bela Bertok
Original assignee: Individual
Current assignee: CHINOIN GYOSYSZER-ES VEGYESZETI TERMEKEK GYARA RT
Priority date: 1995-10-20
Filing date: 1996-10-16
Publication date: 1997-04-24

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 µm size according to figures (II or III) optionally formulated to an insecticide product with additional insecticides and auxiliary materials.

Description

CA 0223~280 1998-04-17 Microencapsulate(l insecticide preparations an(l :1 process for the preparation thereof 5' The invention relates to a microencapsulated insecticide preparation containing as active ingredient isomers of Cypermethrin of the formula I
in a pre-selected ratio, furthermore to a formulated product conf~ining the microencapsulated preparation and to a process for the preparation thereof.
Cypermethrin is a molecule containing 3 asymmetry centres and so it is a rnixture of 8 optical isomers. According to the nomenclature established by Michael Elliott hereinafter we will characterise the configuration of the chiral carbon atom signed with a, with R and S
respectively " Cis " and " trans " designations are covering the steric lS arrangement of the substituents of the cyclopropan ring. We set the configuration of the first carbon atom of the cyclopropan ring in the form of lR or 1 S. Accordingly the lRcisS isomer corresponds to 2,2 dimethyl-( 2',2'- dichlorovinyl) - l(R) -cis- cyclopropan-carboxylic acid -oc(S) - cyano-m-phenoxy-benzyl-ester.
Cypermethrin characterised by formula I. is a well known insecticide (Pest.Man. X. Ed., 178, (1994)) which contains all of the 8 possible isomers of the molecule. Its effectiveness can be increased resp. rendered to more selective by omitting the inactive isomers. Alpha-, beta- zeta-(Pest. Man. X. Ed., 179, 180, 181, (1994)), and theta-Cypermethrins '~5 (Hungarian patent specifIcation No. 198 373) have been developed on this basis. The enumerated products are the active ingredients of commercially available preparations which contain the isomers below:
Alpha - Cypermethrin = lRcisR/l ScisR in a 1 :1 ratio Beta - Cypermethrin= lRcisS/lScisR: lRtransS/lStransR
in a 1:1 _ 4/6 ratio Theta - Cypermethrin = 1 RtransS/l StransR in a 1: 1 ratio Zeta - Cypermethrin = lRcis-transS/lScis-transS, cis/trans _ 4/6 ratio.
In the course of applying the products it turned out quickly that a signi~lcant skin irritation occures caused mainly by the cis isomers.
(Aldbridge W.N.: An assessment of the toxicological properties of pyrethroids and their neurotoxicity, In: Critical Reviews in El1vironmental CA 0223~280 1998-04-17 W O 97/14308 PCT~HU96/00060 Control Vol. ~'~, Issue ~, pp 89-104 (1992)). This effect is the most significant in the case of alpha- Cypermethrin and the weakest at tlleta-5 Cypermethrin. On persons using and contacting with the productseruptions, allergic reactions of individually different strength were observed too, which in the more acute cases were accompanied with shock-like symptoms, e.g. fever, swelling of the cheeks. These symptoms occurred more heavily at persons using the products by occupation.
10 Particularly longer exposition to e.g. pesticides in closed places resulted irritation syrnptoms of longer or shorter duration. According to biological studies Cypermethrin and the analogue pyrethroids are not allergens as such but they are significantly increasing and sensitising the effects of other allergens. These by-effects limit their usage resp. their 15 use requires special care.
Another significant problem of the molecule is that because of having a broad speetrum it is very effective against cold-blooded species and more or less independently from the mode of the application it kills useful creatures as bees, predatory insects, mites etc. too, therefore its 20 selective application in the form of conventional products can not be secured. (Hill, R.; Effect on non-target org7~ni.sm.s in terrestrial and aquatic environment, In: The Pyrethroid Insecticides, Ed. Leahey J.P., pp 151 -26~ (1985) Taylor and Francis, London.).
The situation is further worsened by the significant repellent i.e.
25 frightening effect of the pyrethroids including Cypermethrin and so they can not be used directly or only with little efficacy against hiding pests.
For securing safe handling of dangerous materials, e.g. powerful poisons, explosives procedures were developed in the last decades on the basis of colloid chemical results under the comprehensive narne of 30 microencapsulation (Bungenberg de Jong H D, In. Colloid Sci, Ed.H.R.
~ yt; Elsevier, Amsterdam, Vol.~, p. 249- (1949); J.R. Nixon,ed., Microencapsulation, Marcel Dekker, Inc., New York (1976); T. Kondo, ed., Microencapsulation, Techno Inc., Tokyo, Japan (1979)). The point of this is that on the surface of colloid size granules or droplets a new phase 35 is made, quasi the substance is packed in, by whicll a substance with new characteristics is obtained. This process can be carried out in liquid and in vapour phase, in solution or in melt, it can happen physically by phase separation (coacervation) resp. chemically by interfacial polymerization.
The formed wrapping ~,vall can be solid or semi-solid. The size of the W O 97/14308 3 PCTnHU96/00060 granule can vary from 0,1 - 0,~ ,um to the rnm range, and its shape from regular globe to an irregular form. The active ingredien-t can be imbedded into the granule irregularly, it can have matrix character, or it can be surrounded regularly by the ~vrapping substance. These parameters depend in a large measure from physico-chemical and colloido-rheological characteristics of the system applied and witllin certain limits, 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 given conditions. It is owing to this that microencapsulation procedures were individually developed for different active ingredients, among them for insecticides based first of all on phosphate esters (Controlled Release Pesticides, ACS Symp. Series, No 53, Am. Chem.Soc. Washington, D.C., (1 977)).
In the case of pyrethroids containing isomers which can isomerize in the presence of a base (e.g. ,13-Cypermethrin to o~-Cypermethrin (HU
210.098) rnicroencapsulation may be a very difficult task. That can be the reason why no adequate process has been worked out for such products until now.

Our invention relates specially to rnicroencapsulation of isomer mixtures of Cypermethrin having optimalized composition (first of all beta and theta Cypermethrins) and to the new products obtained this way, which can be used advantageously in the protection of plants, crops and trees, in the veterinary therapeutics as ektoparasiticum, in the public health and in the extermination of "home pests" as mosquitoes, flies, cockroaches, ants, lice, fleas, ticks, termites etc. Although the disadvantages and problems characteristic for Cypermethrin are known long ago and theoretically they could have been elimin~ted by microencapsulation, the development of products within the subject of our invention has not been accomplished until the date of the present application because of the individual character of microencapsulation which depends on the active ingredient. Microencapsulated products cont~ining selected isomers of Cypermethrin were not known previously.
In the products obtained by procedures according to our invention all of the unfavourable features attributable to the contact activity of Cypermethrin isomers can be decreased or ceased by selecting isomer CA 0223~280 1998-04-17 W O 97/14308 4 PCT~HU96/00060 mixtures (e.g. beta and theta Cypermethrin) from the aspects of efficiency and harmlessness. These aspects include but are not limited to decrease S of toxicity exerted on warrn- blooded and aquatic living creatures the latter living in nahlral waters, reducing exposition and effects on hllm~n~
during usage, improvement of selectivity at plant protecting applications, in as much as direct contact efficiency of the products within the protection of our invention is limited to useful Articulata and they exert stomatotoxic effects only on pests feeding on treated plants. They are favourable from the aspect of developing resistance of pests, because by reducing the repellent effect of pyrethroids the uptake of lethal doses is increased. Because of controlled release of their active ingredients the products according to the invention have an increased duration of activity, which is important first of all in professional extermination of pests and in public health. The formulations according to our invention display further advantages in as much as they are water based versus the infl~mm~ble organic solvents used regularly in the formulation of pyrethroids and characterised by high inh~l~tion toxicity, or powders.
The wrapping of the active ingredient made it possible that a staff previously distinctly sensitized to Cypermethrin can directly apply the new products. The acute toxicity measured on warm- blooded creatures decreased too: in the case of a microencapsulated product cont~ining ~5 % beta- Cyperrnethrin the acute per os LDso value for rats was > 5000 mg/kg while in the case of the control Chinmix SSC (aqueous micro suspension cont~ining 5% beta- Cyper~nethrin) the LDso value was 1513.6 mg/kg .
A significant advantage is that by the procedure according to our invention substances can be introduced application of which was impossible or curnbersome by the conventional methods, respectively their coexistence within a preparation was not solvable because of their different physical and chernical indices. By this method attractants, filling and activity enhancing materials, in particular cases further insecticides and other ~ ry substances can be applied according to choice. By repeating the microencapsulation procedure and by introduction of these substances in the desired course a manifold microencapsulation is possible. This way the active ingredient can be coated with an external attractant envelope and products can be prepared which exterrninate only the individuals of a given species or hiding pests.

CA 0223~280 1998-04-17 Because the detergents used for folming colloidal solution can be the same as the surface active agents applied in the end product the S microencapsulation procedure can be carried out also in a way, that the produced microcapsule suspension should provide without isolation, preferably with further ~ ry materials the end product.
In the course of developing our procedure one of our aims was to avoid the use of halogenated solvents and so without limiting the scope 10 of protection of our invention for these processes also alternative methods applying ethyl acetate or petrol ether were worked out. So a large scale manufacture taking into account the protection of the environment became possible.

CA 0223~280 1998-04-17 On the base of the aboves our invention rel:ltes to 5 a microencapsulated insecticide preparation comprising as active ingredient 0.001 - 80 w % lRcisS/lScisR and/or lRtransS/lStransR
isomers or isomer mixtures of Cypermethrin of formula I. beside wall materials optionally together with additional effect enhancing, attractant, filling and auxiliary materials or their mixtures wrapped or imbedded into 10 single or manifold microcapsules of 1-~000 ~Lm size according to figures II. or III. optionally formulated to an insecticide product with additional insecticides and auxiliary materials.

The microencapsulated preparation according to the invention contains 15 beta or theta Cypermethrin as active ingredient, lignin, cellulose derivatives, starch, gelatine, resin, polyamide, polyester, polycarbonate, polyurethane, polyùrea polymers as wall material; insecticide syn~rgellls, preferably piperonylbutoxide or sesame oil as activity enhancer;
pheromones and other attractants; various essential oils, sugars, flour, 20 bran, finely dispersed sawdust, pine-resin, guaiacol, lignin and preferably water or combinations of them; biologically and chemically inert substances as filling materials e.g. finely dispersed cellulose, starch, limestone, silica gel powder, silicic acid, paraffin oil or mixtures of them;
emulgeating and suspending agents as ~lncilizlry materials, e.g. ionic or 25 non ionic tensides respectively stabilizers and/ or salts; pyrethroids e.g.
tetramethrin, alletrin as additional insecticide and if desired further ry materials.

Our invention relates furthermore to a process for preparing 30 microencapsulated insecticide product characterised by form~ ting lRcisS/lScisR and/or lRtransS/lStransR isomers or isomer mixtures of Cypermethrin of forrnula I. as active ingredient with wall materials, if desired with additional activity enhancing, attractant, filling and other ~lxili~ry materials and if desired with additional insecticides to 35 microcapsules of 1-~000 ~lm size according to figures II. or III. by applying coacervation and/or interfacial polymerization method.
According to the coacervation method of the invention the active ingredient, activity enhancer, attractant, filling and auxiliary materials furthermore the wall material are mixed with organic solvent, the mixture is stirred with water if necessary in the presence of a detergent, the CA 0223~280 l998-04-l7 W O 97/14308 7 PCT~HU96/00060 organic solvent is evaporated or precipitated by adding to it additional organic or inorganic coagulant, or by adjusting the pH, the wall of the 5 microcapsules obtained is formed to the desired strength by adding to it if necessary additional netting agents as formaldehyde, glutaraldehyde or propylenoxide, then the suspension is filtered and dried or formulated ~vithout filtration optionally by adding to it additional insecticides and au7~iliary materials in the desired form, or the above processes are 10 repeated with the microcapsules containing suspension by adding to it additioual activity enhancers, attractants, filling and auxiliary materials as described above and from the manifold microencapsulated substance the desired product is formulated as described above.

According to the interfacial polymerization method of the invention the active ingredient, activity enhancer, attractant, filling and auxiliary materials furtherrnore the wall material or a component of the wall material are mixed with organic solvent, the solution is dispersed in water optionally in the presence of a detergent, then on the surface of the 20 formed droplets polymerization or polycondenzation is induced by adding polymerization initiating agent or bi or polyfunctional reagents, the formed wall is formed to the desired strength by adding to it if necessary additional netting agents as formaldehyde, glutaraldehyde or propylenoxide, then the suspension is filtered and dried or formulated 25 without filtration optionally by adding to it additional insecticides and ~llxili~ry materials in the desired form, or the above process is repeated with the rnicrocapsules cont~ining suspension by ~ 1ing to it additional activity enhancers, attractants filling and auxiliary materials as described above and from the manifold rnicroencapsulated substance the desired 30 product is formulated as described above.

Microencapsulation by coacervation and by interfacial polyrnerization can be applied repeatedly, if necessary intermittently or combined.

35 Our invention relates furthermore to a process for the preparation of insecticide products characterised by that the microencapsulated product ~ is forrnulated in the form of suspension concentrate, gel suspension, wettable powder dusting material, or as granules dispersible in water.

CA 0223~280 1998-04-17 Suspension concentrates can be prepared by using water, dispersing agent, preferably sodium-lignin-sulfonate, wetting agent, preferable 5 alkyl-aryl-polyglycolether and dialkyl-succinate salt, antigelation agent, preferable propylenglycol and polysaccharide; gel suspensions by using water and dispersing agent, preferable ethoxylated-propo~ylated block polymer and gelating agent, s~refel~ble polyacrylic acid at pH = 6,5;
wettable powder products by using dispersing agent, preferable aL~yl-aryl-10 naphthalene-sulfonic acid sodium salt, wetting agent, preferable polyoxyethylen - alkyl ether, sliding agent and f~lling agent, preferable kaolin; dusting product by using sliding agent and filling agent, preferable talc and silicic acid.

15 Granules dispersible in water can be prepared from the microencapsuleted products according to the invention by usual wet granulating and d~ying methods, preferable using as dispersing agent alkyl-aryl-sulfonic acid-sodium salt-formaldehyde condensate; as wetting agent dialkyl-sulfosuccinate and as binding - adhesive preferable 20 polyvinyl- pyrrolidone and lactose.

The scope of our invention is demonstrated by the examples without limiting it to them.

Examples:

1) 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 1'00 r/m. 60g beta-Cypermethrin and 30 g ethyl cellulose ("Hercules" N-200, 154 cP ) are dissolved in 463 g of dichloromethane and this solution is poured to the aqueous solution. The reaction mixture is stirred at room temperature 35 for 8 hours then the formed microcapsules are settled, decanted, washed with water, filtered and dried under an infra lamp. The yield is 57.64 g;
white powderlike product. Average size of the granules: 135 ~Lm, assay 64 %.

CA 0223~280 1998-04-17 W O 97/14308 9 PCTnHU96/00060 2) It is proceed as in example 1) with the difference that instead of dichloromethane 354 g chloroform are used. The yield is 57 g; white ,, powderlike product. Average size of ~ranules: 207 ~lm, assay 54.~ %.

3) It is proceed as in example 1) with the dirrel-ellce that instead of dichloromethane 315 g ethyl acetate are used. The yield is 55.4 g; white powderlike product. Average size of granules: 241 ,um, assay 66 %.
Water content: 0.17 %.

4) It is proceed as in example 1) with the difference that instead of using infra lamp the product is dried in open air. The yield is 75 g; white powderlike product. Average size of granules: 267 ,um, assay 40 %.
Water content: 34 %.

5) It is proceed as in exarnple 4) with the difference that as attractant additive before microencapsulation 20 w % sugar is dissolved in distilled water and the procedure is carried out with this solution. The yield is 77.2 g; white powderlike product. Average size of granules: 254 ~lm, assay 9.~ %. Sugar content: 7.7 %. Water content: 35.2 %.

6) It is proceed as in example 1) with the difference that instead of 60 g, 50 g beta - Cypermethrin and as synergizing agent 10 g 30 piperonylbutoxide ( PBO) are used. The yield is 56.2 g; white powderlike product. Average size of granules: ~37 ,um, assay 45.3 %. PBO content:
18 %.

It is proceed as in example 6) with the difference that in place of PBO sesame oil is used as synergizing agent. The yield is 57 g; white powderlike product. Average size of granules: 75.6 ,um, assay 44 %.
Sesame oil content: 19 %.

_ CA 0223~280 1998-04-17 8) Into a 1 I beaker supplied with mixer 700 g. distilled water and 1.2 g sodium-lauril-sulfate are added. The solution is stirred at 1200 r/m . lS g theta- Cypermethrin and 15 g. ethyl cellulose ( "Herc~lles" N-200, 154 cP) are dissolved in 175 ml dichloromethane and this solution is poured to the aqueous one. The mixture is stirred for 8 hours at room temperature then the formed microcapsules are settled, decanted, washed with water, filtered and dried under infra lamp. The yield is 27.4 g; white powder. Average size of granules: 132 ,um, assay 50.8 %.

9) It is proceed as in example 8) with the difference that instead of 15 g, 30 g ethylcellullose are used. The yield is 41 g; white powderlike product. Average size of granules: 239~Lm, assay 32 %.

10) It is proceed as in example 8) with the difference that instead of 15 g, 25 g ethyl cellulose, instead of 15g, 0,25 g theta-Cypermethrin are used. The yield is 27.2 g; white powderlike product. Average size of granules: 118 ,um, assay 1 %.

11) It is proceed as in example 8) with the difference that instead of 15 g, 5 g theta- Cypennethrin and as filling substance 10 g paraffin oil are used. The yield is 26.2 g; white powderlike product. Average size of granules: 123 ~lm, assay 14,1 %. Pa~ oil content: 31 %.

12) Into a 250 ml beaker supplied with stirrer 2.5 g polyvinyl alcohol ~ PVA) (Merck, Mr ~ 72000 ), 57.5 g distilled water a_d 0 05 g sodium-lauryl-sulfate are added. The mixture is stirred at 1200 r/min. 4 g beta-Cypermethrin are dissolved in 5.5 g xylene and this solution is poured to the aqueous one. The mixture is stirred for 10 rninutes at room temperature then 36 ml 20 % sodium sulfate solution is dropped to it.
After stirring for lS minutes the pH is adjusted to 3,5 - 4 with citric acid then the wall of the formed microcapsules hardened by ? ml fonnaldehyde solution, for 1 more hour stirred, the product settled, WO 97/14308 11 PCT/llU~G/00.~0 decanted, washed with water, filtered and dried in air. The yield is 8.2 g;
white powder. Average size of granules: 243 !lm, assa~ 42 %.

13) It is proceed as in example 12) with the difference that instead of xylene 5.5 g aromatol are used. The yield is 8.7 g; white, powderlike product. Average size of granules: ~50 ~lm, assay 37.2 %.
14) It is proceed as in example 12) with the difference that instead of polyvinyl-alcohol (PVA) 2.5 g hydroxypropyl-methyl cellulose are used. The yield is 7.6 g; white powderlike product. Average size of 1 5 granules: 2 1 7 ,um, assay 33 %.

15) It is proceed as in example 12) with the difference that instead of polyvinyl-alcohol 2.5 g of cellulose-acetate-phthalate are used. The yield is 7.9 g; white powderlike product. Average size of granules: 203 ,um, assay 37 %.

16) Into an apparatus supplied with magnetic stirrer 60 g carbamide, 86 g formaldehyde solution and 10 % aqueous ethal1olamine solution are added 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 temperature for ~ hours. 9.5 g of the formed water-soluble carbamide- formaldehyde polymer complex is dissolved in 160 g distilled 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 rnl xylene are added to it. After 10 minlltes stirring the pH of the rnixture is adjusted to 3,5-4 by adding to it aqueous cit~ic acid solution and the~drc~ppmg to ~t 100 g s~di.~l-sll~fate inr a _5 ~,~osolution. In order of strengthening the walls of rnicrocapsules 3 ml formaldehyde solution are added to it then stirred for 1 hour. The product is decanted, washed with water, filtered and dried. The yield is 21 g;
white powderlike product. Assay: 17.2 %. Average size of granules:
168 ~lm.

-WO 97/14308 1- PCTnHU96/00060 17) It is proceed as in exarnple 16) with the difference that instead of formaldehyde I g glutaraldehyde is used. The yield is 19. 8 g; white powderlike product. Average size of granules: 16~ ,um, assay 16.9%.

18) Into a 100 ml beaker supplied with Tura~ mixer 40 g 0,5 ~/O PVA
solution and 4 g Dispergens A detergent are added. After stirring at 3800 r/m a solution of 4 g beta-Cypermethrin, 1,8 diphenyl-methane-diisocyanate solved in 8 g xylol are added and stirred for additional 5 rninutes. To the mixture a 40 % water solution of 1,4 g hexamethylene-mine are added and it is stabilized with 1 g polyethyleneglycol after some minutes stirring. The pH of the mixture is adjusted to 5-5,5 by 33 %
fonnic acid solution. The product is used directly. Average size of granules: 4,8 ,um.

19) It is proceed as in example 18) with the difference that instead of diphenyl-methane-isocyanate ONGRONAT CR 30-~0 is used.
Average granule size: 8,0 ~un.

20) Into a 50 ml beaker supplied with Turax mi~er 16.5 g distilled water and 0.67 g MADEOL OR/95 BA detergent are added. Af~ter stirring at 8000 r/m the solution is cooled to 5~C. 4.26 g beta-Cypermethrin and 1.03 g PAPI~27 are dissolved in 8.51 g aromatol then this solution is poured to the aqueous one. The m- ixture is stirred for 6 minutes then 1.43 ml of 43.2% hexamethylene-~ mine solution are dropped to it. After stirring for 3 more min~ltes the pH of the mixture is adjusted to 5-5,5 by 33% forrnic acid solution. The product is used directly. Average size of granules: 1.4,um.

It is proceed as in example 20) ~vith the difference that instead of hexamethylene-~ mine solution 1.03 ml 4~ % aqueous diethylene-triamine solution are used. Average granule size: 4.4 ~lm.

CA 0223~280 1998-04-17 ~) It is proceed as in exarnple 0) with the difference that instead of hexamethylene-diamine solution 2.06 ml of 11 % aqueous 2,5-dimethyl-2,5-hexanediol solution are used. Average size of granules 2.6 !lm.

23) It is proceed as in example 20) with the difference that instead of hexamethylene-diamine solution 2.06 ml of 42.3 % aqueous malonic acid solution are used. Average size of granules: 2.8 ~lm.

24) It is proceed as in example 20) with the difference that instead of hexamethylene-diamine solution 0.6 ml triethanolamine are used and 0.75 g PBO synergetizing substance are added to the active ingredient.
Average size of granules: 2.3 !lm.

~5) It is proceed as in example 20) with the dirrelellce that Atlox is used as detergent. Average size of granules: 1.5 ~lm.

26) Into a beaker supplied with Turax stirrer 25 ml 0.5 % PVA solution and 0.1 g Wettol detergent are added. While stirring the solution at 8000 r/m the temperature is cooled to 5~C. 2 g beta-Cyperrneth~in and 2g sebacic acid chloride are dissolved in 3 g xylene then this solution is poured to the aqueous one. The mixture is stirred for 6 minutes then a solution prepared by dissolving 0.75 g ethylenediamine and 1.2 g diethylene(li~mine in 10 ml water is dropped to it. The product which is used directly is stabilized at the end of the reaction by ~ ling to it 5 ml 25 % sodium sulfate solution.
Average size of granules: 5.7 ~Lm.

- 35 ~7) It is proceed as in example 2~) with the difference that instead of sebacic acid chloride 2 g of 2,4- toluene-diisocyanate and as detergent 0.36 g MADEOL are used. Average size of granules: 4.6 llm.

CA 0223~280 1998-04-17 W O 97/14308 14 PCTnHU96/00060 ~8) It is proceed as in example '~7) with the differe-nce that instead of S xylene kerosene is used as solvent. Average size of granules: 3.5 ,um.

~9) Into a beaker supplied with stirrer ~0 ml of distilled water, 0.4 g Wettol are added then the solution is mixed at 1~00 r/min. 4 g beta-Cypennethrin and 0.4 g PAPI in 4 ml xylene are dissolved, then the solution is added to the aqueous one. After stirring for 15 minutes ~ ml 4 .3 % aqueous HMDA solution are added to it. It is stirred for 5 n~inutes then the pH of the mixture is adjusted to 5-5,5 by a 33 % forrnic acid solution. The gained product is decanted, washed with water, filtered and dried. The yield is 4.2 g; white powderlike product. Assay: 44 %.
Average size of granules: 67 llm.

30) It is proceed as in e~ample '~9) with the difference that as the aqueous phase 150 ml 0.5 % PVA solution and as the organic phase 6 g beta-Cypermethrin and 6 g sebacic acid chloride dissolved in 38 g dichloromethane are used. The wall of the capsules is developed by applying 6 ml 42.3 % HMDA solution. The yield is 14 g; white powder.
Average size of granules: 73 llm. Assay: 31 %.
31) It is proceed as in example 29) with the difference that 150 ml 0.5 %
starch solution is used as protecting colloid. The yield is 12.7 g; white po~vder. Average size of granules: 85 ~m. Assay: ~9 %.
3~) Preparation of gel To 1500 g product prepared according to example 1) 1300 g water and 100 g naphthalene sulfonic acid formaldehyde sodium salt are added after 3 minutes stirring to the suspension 30 g propylenoxide-ethylenoxide adduct (Pluronic P65, BASF) were added. After stirring for '~ rninutes 30 g polyacrylic acid (Carbopol 940) are added to the mixture then the pH is adjusted to 6.5 by applying 1 N NaOH solution.

CA 0223~280 1998-04-17 W O 97/14308 15 PCTnHU96/00060 33) Preparation of suspension concentrate (FW) To 900 g product prepared according to example-8) 900 g water and 38 g sodium lignin sulfonate are added under the mixing conditions of example 30).

Then - 15 g nonylphenol - polyglycolether ( EO = 10 ) - 10 g dioctyl-sulfosuccinate sodium salt - 7 g propylenglycol and - 32 g ~ % Xanthan gum aqueous solution are added successively, with S
minute stirring Intensive stirring is continued for S minutes after adding Xanthan gum.
34) Preparation of wettable powder product ( WP ) To 500 g capsules prepared according to example 16), while stirring it continuously in a Lodige mixer of S 1 working volume 55 g aLkyl-naphthalene sulfonic acid sodium salt,35 g polyoxyethylene alkyl ether, 15 g synthetic silicic acid ( Aerosil 300 ), and 395 g kaolin are added successively. Homogenization is continued for S minutes.

35) Preparation of dusting powder ( P) To S00 g product prepared according to example 29) while stirring it continuously in a Lodige mixer of S 1 working volume 300 g talc, 275 g silicic acid ( Wessalon ) and 25 g synthetic silicic acid (Aerosil 200) are added successively. Mixing is continued for 5 nunutes.

36) Preparation of water - dispersible granules (DG) Tnto a Lodige mixer of S 1 working volume under continuous stirring 850 g product prepared according to example 16) and then - 85 g naphthalene sulfonic acid sodium salt formaldehyde concentrate - 15 g dioctyl sulfosuccinate - 50 g polyvinyl-pyrrolidone( PVP K30) dissolved in 175 ml water - 35 - 50 g lactose are added successively.
15 minutes after feeding the solution the stirring is stopped. The wet ~ powder mixture is formed to granules in a pan granulating equipment of 550 mm diameter. The obtained product is dried in a vacuum drying oven at 55~C for approx. 2 hours to constant weight.

CA 0223~280 1998-04-17 37) Residual efficacy against house fly (Musca domestica) Residual efficacy of the products prepared according to examples 5 33) and 34) on different surfaces and against home fly (Musca domestica WHO/SRS) is demonstrated by the example below. The water diluted products were sprayed to tiles and boards in the given doses with the help of Potter spraying towers . The treated surfaces are kept in dark and at ~5~C and 50-60 RH until using them. Tests were carried O~lt in hvo 10 repetition using 10 -10 ~nim~l~ in each dose every time on surfaces previously not used. The insects are exposed to the treated surfaces for 30 rninutes then placed into clean petri dishes and fed with a food consisting water and sugar ad libitum. Mortality was evaluated after 24 hours in the case of flies and after 48 hours in the case of cockroaches.
15 The values were expressed as percent mortality.
The results show that the products prepared according to exarnples 33) and 34) gave 100-% efficiency for 15 weeks on both types of surfaces.
This is h~o times couger then the standard Coopex 25 WP (6 weeks).

CA 02235280 l998-04-l7 Resiclual ef~;ciencv of tested products a_ainst home flies on tiles Product active in~red. treated surface "a~e" in weeks dose(mcg/m~)) O ¦'~ 14 16 18 ¦ lO ¦ 1~ ¦ 15 1~o 1'~5 '~4 hour mortality ~/o af er 30 minutes of exposition Coope:; ~SWP* ]00 100 lOO lOO lOO 90 85 40 15 O O
E::ample 33) '5 100 lOO ~00 lOO 100 lOO lOO ]00 lOO lOOExample 34) ~5 lOO 100 lOO lOO lOO lOO lOO lOO lOO lOO
lo *contains Permethrin as active ingredient Residual efficiencv of tested products a~ainst home flies on board Product active inc~red. treated surface "as~e" in wee~;s dose(m~/m'~) ~ ¦-' 14 16 l~ llo 11~ 115 ¦~o ¦~S
~4 hour mortalit~ ~/i af-.er 30 minutes of ~-xposition Coopex '5WP* lOO 100 lOO lOO 85 75 35 lO lO S O
Example 33) 50 lOO lOO lOO lOO lOO lOO lOO 100 lOO lOO
Example 34) ''5 lOO 100 lOO lOO lOO lOO lOO lOO lOO lOO*contains Permethrin as active ingredient Residual efficiencv of tested produc-s against coc~roaches (Blattella C~ermanica) on tiles Product active in_red. treated surface "a~e" in weel;s dose ( m~/m'~) O ¦ '2 1 4 1 6 1 8 ¦ lO ¦ 1'' ¦ 15 l ~o 1 '>5 ~4 hour mortalitv % a~er 30 minutes of cxposition Coopex''5W'P* ''00 lOO lOO 100 lOO lOO 75 60 30 0 0 KordonlOWP** 50 lOO lOO lOO lOO lOO 100 95 90 85 40 Chinmix 5SC*** '~5 lOO lOO lOO lOO 100 100 lOO 100 90 65 E~ample 33) '75 100 100 100 lOO 100 lOO 100 lOO 100 lOO* contains Permethrin as active ingredient ** contains Cypermethrin as active ingredient *** contains Beta - Cypermethrin as active ingredient _ Kesidual efficlenc~ of tested produc.s a~Sainst cock~oaches (Blattella ~ermanica) on board Product active ingred. treated su~face "a<Je" in weeks dose(m~/m~) O ¦~ 14 16 18 ¦10 ¦~ 5 l~o 1~5 '~4 hour mortalitv % af~er 30 minutes of e~position Coopex ~5WP~ IOQ IOQ 100 100 80 70 40 ~0 ~ O O
~ordonlOWP*~ 50 lOO lOO lOO lOO lOO 75 50 65 ~5 5 ChinmiY 5SC*** '~5 100 lOO lOO lOO IOQ ]00 8~ 7~ 50 ~$0 Example 33) '~5 lOO 100 lOO 100 100 lOO lOO l~:)O lOO 100 * contains Permethrin as active ingredient ** contains Cypermethrin as acti~e ingredient *** contains Beta - Cypermethrin as active ingredient 36) Residual efficacy against cockroaches (Blattella gerrnanica ) Residual efflcacy of the products prepared according to e~;amples 33) and 34) is demonstrated on different surfaces and against cocl~roaches (Blattella gerrnanica) by the example below.
Surfaces were treated as described in example 37). Products prepared according to examples 33) and 34) have shown a 100 % effectiveness through '75 weeks when applied at ~ mg/m~ dose on tiles and on board.
This is t vo times cuger then the efficiency of Coope~ WP at '~00 m~r/m'' dose and of Kordon 10 WP at 50 mg/m~ dose (8 and 4 resp. 10 and 8 weeks).

Reagents applied:
TWEEN ~0- polyoxyethylene- ~0- sorbitane - monolaur~ late MADEOL AG/OR 95 - naphthalene - sulfonic acid PAPI ~7 - polymethylene- polyphenylene- isocyanate Atlox- polyoxyethylene- sorbitol- hexaoleate Wettol - Phenol sulfonic acid - sodium salt HMDA - Hexamethylene~ mine ONGROMAT CR 30-~0 - polymethylene- pol~/phenylene-isocyanate, 4,4-diphenyl-methane-diisocyallate (MDI)

Claims

1. A microencapsulated insecticide product comprising as active ingredient 0.001-80 w % 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 µm size according to figures II. or III. optionally formulated to an insecticide product with additional insecticides and auxiliary materials.

2. Microencapsulated product according to claim 1. containing beta- or theta- Cypermethrin as active ingredient.

3. Microencapsulated product according to claim 1. containing as wall material of the microcapsules lignin, cellulose derivatives, starch, gelatine, resin, polyamide, polyester, polycarbonate, polyurethane, or polyurea polymer.

4. Microencapsulated product according to claim 1. containing as activity enhancer insecticide synergizing agent, preferably piperonyl-butoxide or sesame oil.

5. Microencapsulated product according to claim 1. containing as attractant pheromones, different odorants, sugars, flour, bran, finely dispersed sawdust, pine resin, guaiacol, lignin and preferably water or combinations of them.

6. Microencapsulated product according to claim 1. containing as filling material biologically and chemically inert substances, preferably finely dispersed cellulose, starch, limestone, silica powder, silicic acid, paraffin oil or mixtures of them.

7. Microencapsulated product according to claim 1. containing as auxiliary material emulsifying and suspending agents, preferably ionic or non-ionic tensides, stabilizers and/or salts.

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

9. A process for the preparation of microencapsulated insecticide products which comprises formulating 1RcisS/1ScisR and/or 1RtransS/1StransR isomers or isomer mixtures of Cypermethrin of formula I. as active ingredient with wall materials and optionally with additional activity enhancing, attractant, filling and other auxiliary materials and with additional insecticides to microcapsules of 1- 2000 µm size according to figures II. or III. by applying a coacervation and/or interfacial polymerization method.

10. A coacervation process according to claim 9. which comprises mixing the active ingredient, activity enhancer, attractant, filling and auxiliary materials, and the wall material with organic solvent, mixing the mixture so obtained with water if desired in the presence of a detergent, evaporating the organic solvent or precipitating it by adding to it additional organic or inorganic coagulant, or by adjusting the pH, forming the wall of the produced microcapsules to the desired strength by adding to it if desired additional netting agents as formaldehyde, glutaraldehyde or propylenoxide, then filtering and drying the suspension or transforming it into the product without filtration optionally by adding to it additional insecticides and auxiliary materials, or repeating the above process with the microcapsule containing suspension by adding to it additional activity enhancers, attractants, filling and auxiliary materials and transforming the manifold microencapsulated substance to the product.

11. An interfacial polymerization process according to claim 9 which comprises mixing the active ingredient, activity enhancer, attractant, filling and auxiliary materials and the wall material or a component of wall material with organic solvent, dispersing the solution in water if desired in the presence of a detergent, then inducing polymerization on the surface of the formed droplets by adding polymerization initiating agent or bi or polyfunctional reagent, developing the formed wall to the desired strength by adding to it if desired additional netting agents as formaldehyde, glutaraldehyde or propylenoxide, then filtering and drying the suspension or transforming it to the product without filtration optionally by adding to it additional insecticides and auxiliary materials, or repeating the above process with the microcapsule containing suspension by adding to it additional activity enhancers, attractants, filling and auxiliary materials and transforming the manifold microencapsulated substance to the product.

12. Process according to claims 9. -11. which comprises repeating coacervation and interfacial- polymerization microencapsulation several times, if desired intermittently or combined.

13. Process for the preparation of an insecticide product which comprises formulating the microencapsulated product of claim 1 as suspension concentrate, gel suspension, wettable powder product, dusting product, or water-dispersible granules.

14. Process according to claim 13. which comprises preparing the suspension concentrate by using water; dispersing agent, preferably sodium lignin sulfonate; wetting agent preferably alkyl-aryl-polyglycolether, dialkyl-succinate salt; antigeling agent, preferablepropylenglycol or polysaccharide.

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

16. Process according to claim 13. which comprises preparing wettable powder product by using dispersing agent, preferably alkyl-aryl-naphthalene-sulfonic acid- sodium salt; wetting agent, preferably polyoxyethylene-alkyl ether; sliding agent and filling substance, preferably kaolin.

17. Process according to claim 13. which comprises preparing dusting product by using sliding agent, filling substance, preferably talc and silicic acid.

18. Process according to claim 13. which comprises preparing water-dispersible granules by using usual wet granulation and drying methods, and as dispersing agent preferably alkyl-aryl-sulfonic acid- sodium salt- formaldehyde concentrate; as wetting agent dialkyl-sulfosuccinate and as binding agent and adhesive preferably polyvinyl- pyrrolidone and lactose.