BG102463A - Microcapsulated insecticidal product and method for its preparation - Google Patents

Abstract

The invention relates to a microcapsulated insecticidalproduct containing, as active component, from 0.001 to 80 wt.%1RcisS/1ScisR and/or 1RtransS/1StransR isomers or isomer mixturesof cipermetrine with the formulato a barrier material, optionally used together with substanceswhich additionally increasing the activity coaxing substances,fillers and additives ot mixtures thereof which are enveloped orbuilt-in into one-layer or multilayer microcapsules sized from 1to 2000 m, optionally prepared in the form of insecticidalproduct together with additional insecticides and additives.18 claims

Description

The invention relates to a microencapsulated insecticidal product containing as active ingredient isomers of cypermethrin of formula I in a pre-selected ratio as well as to a ready-to-use formulation containing the microencapsulated preparation and to a process for its preparation.

Cypermethrin has a molecule that contains 3 asymmetric centers, so that it is a mixture of 8 optical isomers. According to Michael Elliott's nomenclature, the configuration of the chiral carbon is further characterized by reference to the

a, with R and respectively with S, as well as with cis and trans, which designates the etheric arrangement of the substituents to

are the 8 possible isomers of your molecule. Their efficiency can be increased, and accordingly their selectivity can be modified by avoiding inactive isomers. For this cyclopropane ring. The configuration of the first carbon atom of the propane ring is here defined as Form 1R or 1S. Accordingly, the 1 RcisS isomer corresponds to 2,2-dimethyl (2 ', 2' - dichloro nyl) - (R) -cyclo-cyclopropane-carboxylic acid in- (B) -cyano-t-phenoxy-benzyl ester.

The cypermethrin represented by Formula I is a well-known insecticide (Pest. Man. X. Ed., 178, (1994), which contains all ·· ····

alpha-, beta-, ceta- (Pest. Man. X. Ed., 179, 180, 181, (1994)) and theta-cypermethrins (Hungarian Patent No. 198 373) were obtained. The aforementioned products are active ingredients of commercially available preparations containing the isomers listed below:

Alpha-cypermethrin = 1 RcisR / 1 ScisR in 1: 1 ratio.

Beta-cypurmethrin = 1 RcisS / 1 ScisR: 1 RtransS / 1 StransR in a ratio of 1: 1 to = 4/6.

Theta-cypermethrin = 1 RtransS / 1 StransR in a 1: 1 ratio.

Ceta-cypermethrin = 1Rcis-transS: 1Scis-transS in the ratio cis / trans = 4 / Q.

In the course of product administration, it has been quickly established that significant irritant effects on the skin are caused mainly by the cis isomers (Aidbridge WN: An assessment of the toxicological properties of pyrethroids and their neurotoxicity, in Critical Reviews in Environmental Control Vol 22, Issue 2 This effect is most pronounced in alpha-cypermethrin and lowest in theta-cypermethrin, when people who use and come into contact with the product's rash have allergic reactions, which are individually different in strength have also been found to be in most cases of acute herds are accompanied by shock-like symptoms, such as chills, swollen cheeks, which are more common in people who use the product professionally, especially when exposed to pesticide for long periods of time, ie when the pesticide is indoors. According to biological studies, cypermethrin, as well as similar pyrethroids, are not allergens per se, but they significantly increase the sensitivity to the effects of · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 9 9 · · · · · · · · · 9 9 9

999 99 99 999 99 99 other allergens. These side effects determine their use, respectively, their use requires special care.

Another significant problem with cypermethrin is that, because its molecule has a very wide spectrum, it is very effective against cold-blooded species and more or less, regardless of the mode of administration, it destroys useful creatures such as bees, predatory insects, worms, etc., so selective application in the form of known products cannot be ensured. (Hill, R.; Effect on non-target organisms in terrestrial and aquatic environments, in The Pyrethroid Insecticides, Leahey J.P., pp. 151-262 (1985), Taylor and Francis, London).

The situation is further exacerbated by the significant repulsion, ie the effect of the threat of the use of pyrethroids, including cypermethrin, and the fact that they cannot be used directly or only with low efficacy against hidden pests.

To provide storage for the use of hazardous materials, e.g. strong poisons, explosives, in recent decades, methods have been developed based on colloidal chemistry leading to the so-called microencapsulation (Bungenberg de Jong N D, Colloid Sci, Ed. HR Kruyt; Elsevier, Amsterdam, Vol. 2 p.). 249 et seq. (1949); JR Nixon, ed., Microencapsulation, Marcel Dekker, Inc., New York (1976)); T. Kondo, Microencapsulation, Techno Inc., Tokyo, Japan (1979). The main thing about them is that a new phase is created on the surface of the granules or droplets of colloidal size, as if the substance was packed with it to produce a substance with new characteristics. This process can be carried out in a liquid • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · It can be carried out physically by phase separation (coacervation) or by chemical means by interfacial polymerization. The wall enclosure formed may be solid or semi-rigid. The size of the granules may range from 0.1 to 0.2 μηη to mm and their shape ranges from well-shaped globules to uneven. The active substance may be incorporated into the granules irregularly, may have the character of a matrix, or may be arranged evenly through the envelope. These parameters depend to a large extent on the physicochemical and colloid-rheological characteristics of the system used, and to some extent, depending on the desired purpose, are determined by the technique and technology used. Accordingly, microencapsulation is a general method that needs to be specifically investigated and developed under the given conditions. Due to the fact that microcapsule methods are developed individually for different active substances, among them insecticides are primarily based on phosphate esters (Controlled Release Pesticides, ACS Symp. Series, No 53, Am. Chem. Soc. Washington , DC, (1977).

In the case of working with pyrethroid-containing isomers that can be isomerized in the presence of a base (eg β-cypermethrin to α-cypermethrin (HU 210 098)) microencapsulation can be a very difficult task. This may be why a suitable method for such products has not been developed so far.

The present invention relates in particular to micro-encapsulation of isomeric mixtures of cypermethrin having an optimized composition (especially beta and theta-cypermethrins) and to novel products thus obtained which can be

used with preference for the protection of plants, crops and trees, in veterinary medicine such as ectoparasiticides, in public health and for the eradication of domestic pests such as mosquitoes, flies, cockroaches, ants, lice, ticks, termites, etc. Although the disadvantages and problematic characteristics of cypermethrin have been known for a long time and they can theoretically be eliminated by microencapsulation, the creation of products thereof, which is a task of the present claim, was not accomplished by the date of the present invention due to the individual nature of the microencapsulation, which depends on the active substance. Microencapsulated products containing selected isomers of cypermethrin are not known before this invention.

In the products obtained by the method of the present invention, all of the undesirable properties inherent in the contact activity of the cypermethrin isomers can be reduced or prevented by the selection of isomeric mixtures (eg beta- and theta-cypermethrins) in terms of efficacy and harmlessness. These aspects include, but are not limited to, the reduction of toxicity to warm-blooded and water-dwelling creatures living in natural waters, and the reduction of exposure to human exposure during use of the preparations, to the improvement of selectivity for crop protection applications, insofar as the efficacy of direct contact of the sheath products according to the present invention does not occur on the beneficial arthropods and they exert stomatotoxicity effects only on pests feeding on treated crops. These preparations are also preferable from the point of view of the development of pesticide resistance, as the lethal dose is increased by reducing the repulsive effect of the peroids. Due to the controlled release of their active components, the products according to the invention have an increased duration of activity, which is particularly important for the professional use of pesticides and for public health. The formulations according to the invention also have the advantage that they are water-based over the highly flammable organic solvents commonly used in the pyrethroid administration forms, which have high inhalation toxicity or powder forms.

The active substance coating enables staff who were previously sensitive to cypermethrin to directly administer new products. The acute toxicity measured in warm-blooded creatures is also reduced: in the case of administration of a microencapsulated product containing 25% beta-cypermethrin the acute LDgQ value per rat in rats is> 5000 mg / kg, whereas in the case of control with the Chinmix 5SC preparation (aqueous microsuspension, containing 5% beta-cypermethrin) The 10-value is> 1513.6 mg / kg.

A significant advantage of the invention is that by the method according to the invention, the substances can be administered in a manner which was impossible or difficult by known methods, respectively, their simultaneous application in the preparations was not possible due to their insolubility due to the different physical and chemical indicators. In this method, lures, fillers, and activity enhancing materials, c

• In specific cases, other insecticides and other additives may be optional. By repeating the microencapsulation method and introducing these substances into the desired layer, multilayer microencapsulation is possible. In this way, the active substance can be covered by an exterior lure and products can be obtained that destroy only certain individuals of particular species or hidden pests.

Since the surfactants used to prepare the colloidal solution may be the same as the surfactants applied in the final product, the microencapsulation method can also be conducted in such a way that the resulting suspension containing microcapsules and provide the final product without insulation, preferably with other additives.

In developing the present method, one of the purposes is to avoid the use of halogenated solvents and thus without limiting the scope of protection of the present invention, alternative methods using ethyl acetate or petroleum ether have also been developed to carry out this process. In this way, a wide range of advantages can be taken into account, including enabling environmental protection through a wide range of derivatives.

Based on the foregoing, the invention relates to a microencapsulated insecticidal product containing as active ingredient 0.001 to 80 wt. % 1 RcisS / 1 ScisR and / or 1 RtransS / 1 StransR isomers or isomeric mixtures of cypermethrin of formula I to the barrier materials, optionally together with the activity enhancers, lures, fillers and additives or mixtures thereof, coated or

incorporated in single or multilayer microcapsules of size 1 to 2000 μπτ according to Figures II and III, optionally prepared in the form of an insecticidal preparation together with additional insecticides and additives.

The microencapsulated preparation according to the invention contains, as active ingredient, beta- and theta-cypermethrin; lignin, cellulose derivatives, starch, gelatin, resins, polyamides, polyesters, polycarbonates, polyurethanes, polyurea

our polymers as barrier materials; insecticidal synergists, preferably piperronyl butoxide or sesame oil, to increase activity; pheromones and other lures; various essential oils; sugars, flour, bran, sawdust, pine resin, guaiacol, lignin and preferably water or a combination thereof; biologically or chemically inert substances such as excipients, e.g. finely dispersed cellulose, starch, limestone, silica gel powder, silicic acid, paraffin oil or mixtures thereof; emulsifying or suspending agents such as additives, e.g. ionic or non-ionic surfactants, respectively stabilizers and / or salts; pyrethroids, e.g. tetrametrin, aletrin as additional insecticides and, if desired, other additives.

The present invention also relates to a process for the preparation of a microencapsulated insecticidal product, characterized in that a formulation is prepared comprising as active ingredient 1 RcisS / 1 ScisR and / or

RtransS / IStransR isomers or isomeric mixtures of cypermethrin of formula I to barrier materials, if desired, together with materials with additional activity-enhancing effect, lures, fillers and additives and, if desired,

additional insecticides to obtain microcapsules of size 1 to 2000 µm according to Figures II and III by applying coacervation and / or boundary (at the boundary between two phases) polymerization method.

By the method of coacervation according to the invention, the active substances, the activity enhancers, the lures, fillers and additives, as well as the material forming the partition wall are mixed in an organic solvent, the mixture is stirred with water, if necessary in the presence of surfactants, the organic solvent is evaporated or precipitated by adding additional organic or inorganic coagulant to it or by adjusting the pH, the resulting encapsulation of the microcapsules is formed to the desired strength by adding optional cross-linking agents, such as formaldehyde, glutaraldehyde or propylene oxide, after which the suspension is filtered and dried or converted to the desired form without filtration, in particular by the addition of additional insecticides and additives, or the above processes are repeated with microcapsules containing the suspension by adding to it additional active activity enhancers, lures, fillers and additives, as described above and from the obtained m ogosloyno microencapsulated substance to give the desired composition for use in the manner described above.

By the method of boundary polymerization according to the invention, the active substance, the activity-enhancing agents, the lures, the fillers and the additives, as well as the material forming the barrier or the components of the material from which the barrier is formed, are mixed in an aqueous solution.

the solution is dispersed in water, in particular in the presence of surfactants, then polymerization or polycondensation is induced on the surface of the droplets obtained by the addition of a polymerization initiating agent or by di- or polyfunctional reagents, the resulting barrier being treated of the desired strength by adding, if necessary, additional cross-linking agents such as formaldehyde, glutaraldehyde or propylene oxide, then the suspension is filtered and dried or converted to a The non-filtrate administration form, in particular when additional insecticides and additives are added, or the processes described above are repeated with a suspension containing microcapsules by adding to it additional activity-enhancing agents, lures, fillers and additives, as well as is described above and from the resulting multilayer microencapsulated substance the desired preparation is obtained in the manner described above.

Microencapsulation by co-preservation and by boundary polymerization can be applied repeatedly, if desired with interruptions or in combination.

The present invention also relates to a method for preparing an insecticidal product, characterized in that the microencapsulated product is prepared in the form of a suspension concentrate, a gel suspension, a wettable powder for dusting or as water-dispersible granules.

Suspension concentrates can be prepared using water, a dispersing agent, preferably sodium ligninsulfonate, a wetting reagent, preferably an alkyl aryl polyglycoleter and a dialkyl succinate salt,

anti-gelling reagents, preferably propylene glycol and polysaccharides, gel suspensions using water and a dispersing agent, preferably epoxylated-propoxylated block copolymer and gelatinizing reagent, preferably polyacrylic acid at pH 6.5; capable of wetting powder products using a dispersing agent, preferably an alkylaryl naphthalenesulfonic acid sodium salt, a wetting reagent, preferably a polyoxyethylene alkyl ether, a lubricant and a filler, preferably kaolin; a dusting agent using a lubricant and a filler, preferably talc and silicic acid.

Water-dispersible granules can be prepared from the microencapsulated products of the invention by conventional wet granulation and drying methods, preferably using alkylaryl sulfonic acid-sodium salt-formaldehyde condensate as a dispersing agent; as a wetting reagent, preferably dialkylsulfosuccinate is used, and polyvinylpyrrolidone and lactose are preferably used as a binding adhesive.

The scope of the present invention is demonstrated by, but not limited to, the following examples.

Examples of carrying out the invention

Example 1

Mix a 1400 g distilled water and 1.5 g sodium lauryl sulfate in a 2 liter beaker equipped with a stirrer. The solution was stirred at 1200 r / m. A solution of 60 g of beta-cypermethrin and 30 g of ethylcellulose (Hercules N-200, 154 cP) was prepared in 463 g of dichloromethane, and this solution was poured into an aqueous solution.

CMI ··

The reaction mixture was stirred at room temperature for 8 hours and the resulting microcapsules were precipitated, decanted, washed with water, filtered and dried under an infrared lamp. The yield was 57.64 g of a white powder-like white product. Average granule size: 135 µm. Analysis: 64%.

Example 2

The test was carried out according to the method described in Example 1, except that 354 g of chloroform was used instead of dichloromethane. The yield is 57 g of a white powder-like product. Average granule size: 207 µm. Analysis: 54.2%.

Example 3

The test was carried out by the method described in Example 1, except that 315 g of ethyl acetate was used instead of dichloromethane. 55.4 g of a white powder-like product are obtained. Average granule size: 241 µm. Analysis: 66%. Water content: 0.17%.

Example 4

The test is carried out according to the method described in Example 1, except that the product is dried instead of an infrared lamp under open air access. 75 g of a white powder-like product are obtained. Average granule size: 267 μηη. Analysis: 40%. Water content: 34%.

Example 5

The assay was carried out according to the method described in Example 4, except that 20 wt% was added as a luring additive before microencapsulation. % sugar dissolved in distilled water and the process is carried out with this solution. A yield of 77.2 g of a white powder-like product was obtained. Average granule size: 254 µm. Analysis: 9.2%. Sugar content 7.7%.

Water content: 35.2%.

Example 6

The assay was carried out according to the method described in Example 1, except that instead of 60 g, 50 g of beta-cypermethrin was used and piperronyl butoxide (PBO) was used as a synergistic agent. A yield of 56.2 g of a white powder-like product was obtained. Average granule size: 237 µm. Analysis: 45.3%. Piperonyl butoxide content 18%.

Example 7

The experiment was performed according to the method described in Example 6, except that the method used as a synergistic agent was sesame oil instead of piperinyl butoxide. A yield of 57 g of a white powder-like product was obtained. Average granule size: 75.6 μιη. Analysis: 44%. Sesame oil content 19%.

Example 8

Mix 700 g of distilled water and 1.2 g of sodium lauryl sulfate in a 1 liter beaker equipped with a stirrer. The solution was stirred at 1200 r / m. A solution of 15 g of tetacypermethrin and 15 g of ethylcellulose (Hercules N-200, 154 cP) was prepared in 175 ml of dichloromethane, and this solution was poured into an aqueous solution. The reaction mixture was stirred at room temperature for 8 hours and the resulting microcapsules were precipitated, decanted, washed with water, filtered and dried under an infrared lamp. The yield was 27.4 g of a white powder-like product. Average granule size: 132 μιη. Analysis: 50.8%.

Example 9

The test was carried out according to the method described in Example 8, except that 30 g of ethylcellulose was used instead of 15 g.

The yield is 41 g of a white powder-like product. Average granule size: 239 μηη. Analysis: 32%.

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Example 10

The assay was carried out according to the method described in Example 8, except that 25 g of ethylcellulose was used instead of 15 g and 0.25 g of theta-cypermethrin instead of 15 g. The yield was 27.2 g of a white powder-like product. Average granule size: 118 µm. Analysis: 1%.

Example 11

The test was carried out according to the method described in Example 8, except that 5 g of theta-cypermethrin was used instead of 15 g and 10 g of paraffin oil was used as a filler. It turns out

26.2 g of white powder-like product. Average granule size: 123 µm. Analysis: 14.1%. Paraffin content: 31%.

Example 12

In a 250 ml beaker equipped with a stirrer was added 2.5 polyvinyl alcohol (PVA) (Merck, M _d »72000), 57.5 g distilled water and 0.05 g of sodium lauryl sulfate. The mixture was stirred at 1200 r / min. Dissolve 4 g of beta-cypermethrin in 5.5 g of xylene and pour this solution into the aqueous solution. The mixture was stirred for 10 minutes at room temperature and 36 ml of a 20% solution of sodium sulfate was added dropwise thereto. After stirring for 15 minutes, the pH of the solution was adjusted to 3.5 - 4 with citric acid and the formed partitions of the microcapsules were solidified with 2 ml of formaldehyde solution, the mixture was stirred for another hour and the resulting microcapsules were precipitated, decanted, they are washed with water, filtered and air-dried. The yield was 8.2 g of a white powder-like product. Average granule size: 243 μηη. Analysis: 42%.

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Example 13

The assay was performed according to the method described in Example 12, except that 5.5 g of aromatol was used instead of xylene. The yield is

8.7 g of white powder-like product. Average granule size: 250 μητι. Analysis: 37.2%.

Example 14

The test was carried out according to the method described in Example 12, except that 2.5 g of hydroxypropyl methylcellulose was used instead of polyvinyl alcohol. The yield was 7.6 g of a white powder-like product. Average granule size: 217 μηη. Analysis: 33%.

Example 15

The assay was performed according to the method described in Example 12, except that 2.5 g of cellulose acetate-phthalate was used instead of polyvinyl alcohol. The yield was 7.9 g of a white powder-like product. Average granule size: 203 µm. Analysis: 37%.

Example 16

In a apparatus equipped with a magnetic stirrer, 60 g of urea, 86 g of formaldehyde solution and 10% aqueous ethanolamine solution are placed in such a quantity that the pH of the resulting mixture is 7.5. With stirring, the mixture was heated to 70 ° C and held at this temperature for 2 hours. 9.5 g of the resulting water-soluble urea-formaldehyde polymer complex was dissolved in 160 g of distilled water and 0.1 g of the Tween-20 surfactant was added to the solution. With stirring at 1200 r / m, 4 g of beta-cypermethrin dissolved in 5.5 g of xylene was added to this reaction mixture. The mixture was stirred for 10 minutes and the pH of the solution was adjusted to 3.5-4 by the addition of aqueous citric acid and then added to it.

100 g of sodium sulphate dropwise as a 25% solution. In order to strengthen the partition walls of the microcapsules, 3 ml of formaldehyde solution was added and the mixture was stirred for another hour. The resulting microcapsules were decanted, washed with water, filtered and dried. The yield is 21 g of a white powder-like product. Average granule size: 168 µm. Analysis:

17.2%.

Example 17

The assay was performed according to the method described in Example 16, except that 1 g of glutaraldehyde was used instead of formaldehyde. The yield was 19.8 g of a white powder-like product. Average granule size: 168 µm. Analysis: 16.9%.

Example 18

To a 100 ml beaker equipped with a Turax type mixer was added g 0.5% solution of polyvinyl alcohol and 4 g of Dispergens A surfactant. After stirring at 3800 r / m, a solution of 4 g of beta-cypermethrin was added,

1,8 diphenylmethane diisocyanate dissolved in 8 g of xylene and the mixture was stirred for another 5 minutes. To the mixture was added 40% aqueous solution of 1.4 g of hexamethylenediamine and after a few minutes of stirring the mixture was stabilized with 1 g of polyethylene glycol. The pH was adjusted to 5-5.5 by the addition of 33% formic acid solution. The product is used directly. Average granule size: 4.8 µm.

Example 19

The test is carried out by the method described in Example 18, except that diphenylmethane isocyanate is used instead

ONGRONAT CR 30-20. Average granule size: 8.0 µm.

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Example 20

In a 50 ml beaker fitted with a Turax type mixer is added

16.5 g of distilled water and 0.67 g of MADEOL OR / 95 VA surfactant. After stirring at a speed of 8000 r / m, the solution was cooled to 5 ° C. 4.26 g of beta-cypermethrin and 1.03 g of PAPI 227 were dissolved in 8.51 g of aromatol and the mixture was poured into aqueous solution. The mixture was stirred for 6 minutes and added 1.43 ml of a 43.2% solution of hexamethylenediamine dropwise. After stirring for more than 3 minutes, the pH was adjusted to 5-5.5 by the addition of 33% formic acid solution. The product is used directly. Average granule size: 1.4 µm.

Example 21

Work as described in Example 20 except that instead of a solution of hexamethylenediamine 1.03 ml of a 42% solution of diethylenetriamine is used. Average granule size:

4.4 μΠΊ.

Example 22

Work as described in Example 20 except that 2.06 ml of an 11% aqueous solution of 2,5-dimethyl-2,5-hexanediol is used instead of a solution of hexamethylenediamine. Average granule size: 2.6 µm.

Example 23

Work as described in Example 20, except that 2.06 ml of hexamethylenediamine solution is used instead of a solution of hexamethylenediamine.

42.3% aqueous malonic acid solution. Average granule size: 2.8 µm.

Example 24

Work as described in Example 20, except that 0.6 ml is used instead of hexamethylenediamine solution.

triethanolamine and 0.75 g of piperronylbutoxide (PBO) was added to the active substance as a synergistically active additive. Average granule size: 2.3 µm.

Example 25

Work was done as described in Example 20, except that Atlox was used as the surfactant. Average granule size: 1.5 μιτι.

Example 26

25 ml was added to a glass fitted with a Turax mixer

0.5% solution of polyvinyl alcohol and 0.1 g of Wettol surfactant. With stirring at 8000 r / m, the solution was cooled to 5 ° C. 2 g of beta-cypermethrin and 2 g of sebacin chloride were dissolved in 3 g of xylene and the mixture was poured into an aqueous solution. The mixture was stirred for 6 minutes and a solution obtained by dissolving 0.75 g of ethylenediamine and 1.2 g of diethylenediamine in 10 ml of water was added dropwise. The product was used directly, finally stabilizing the reaction by adding 5 ml of 25% sodium sulfate solution. Average granule size: 5.7 µm.

Example 27

The procedure was described in Example 22 except that 2 g of 2,4-toluenediisocyanate was used instead of sebacic acid chloride and 0.36 g of MADEOL was used as the surfactant. Average granule size: 4.6 μηη.

Example 28

The procedure is as described in Example 22 except that kerosene is used instead of xylene as the solvent. Average granule size: 3.5 μιτι.

• · · · · ·

Example 29

To a beaker equipped with a stirrer was added 20 ml of distilled water and 0.4 g of Wettol surfactant and the solution was stirred at 1200 r / min. 4 g of betacypermethrin and 0.4 g of PAPI were dissolved in 4 ml of xylene and the mixture was poured into aqueous solution. The mixture was stirred for 15 minutes and 2 ml of a 42.3% solution of hexamethylenediamine were added thereto. After stirring for 5 minutes, the pH was adjusted to 5-5.5 by the addition of 33% formic acid solution. The resulting product was decanted, washed with water, filtered and dried. 4.2 g of a white powder are obtained. Analysis: 44%. Average granule size: 67 µm.

Example 30

The test was carried out according to the method described in Example 29, except that 150 ml of 0.5% polyvinyl alcohol solution was used as the aqueous phase and 6 g of beta-cypermethrin and 6 g of sebacic acid chloride dissolved in 38 g were used as the organic phase. dichloromethane. The capsule walls were improved by adding 6 ml of a 42.3% solution of hexamethylenediamine. The yield is 14 g of a white powder-like product. Average granule size: 73 µm. Analysis: 31%.

Example 31

Work as described in Example 29, except that 150 ml of 0.5% starch solution was used as a protective colloid. The yield was 12.7 g of a white powder-like product. Average granule size: 85 μιη. Analysis: 29%.

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99999

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Example 32

Gel preparation

To 1500 g of the product obtained as described in Example 1 was added 1300 g of water and 100 g of the naphthalenesulfonic acid formaldehyde-sodium salt and 30 g of propylene oxide-ethylene oxide adduct (Pluronic P65, was added to the suspension for 3 minutes). BASF). After stirring for 2 minutes, 30 g of polyacrylic acid (Carbopol 940) was added to the mixture and the pH was adjusted to 6.5 by the addition of 1N sodium hydroxide solution.

Example 33

Preparation of suspension concentrate (FW)

To 900 g of the product obtained according to Example 8 was added 900 g of water and 38 g of sodium ligninsulphonate under the stirring conditions described in Example 30.

It is then added sequentially

- 15 g of nonylphenol-polyglycol ether (EC = 10),

- 10 g of dioctyl sulfosuccinate sodium salt,

- 7 g propylene glycol and

- 32 g of a 2% aqueous xanthan gum solution with vigorous stirring for 5 minutes.

Intense stirring was continued for 5 minutes after the resin was added.

Example 34

Getting Wet Powder (WP)

To 500 g capsules prepared according to Example 16, with continuous stirring in a 5 liter Lodige mixer, 55 g of sodium naphthalenesulfonic acid, 35 g of polyoxyethylene 21 alkyl ether, 15 g of synthetic silicic acid (Aerosil 300) and 35 g of synthetic silicic acid were added successively. g kaolin. The homogenization was continued for 5 minutes.

Example 35

Receiving Dust Powder (P)

To 500 g of the product obtained according to Example 29, with stirring in a 5 liter Lodige mixer, were added successively 300 g of talc, 275 g of silicic acid (Wessalon) and 25 g of synthetic silicic acid (Aerosil 300). Stirring is continued for 5 minutes.

Example 36

Preparation of water dispersible granulate (DG)

In a 5 liter Lodige mixer, 850 g of the product obtained in Example 16 was added sequentially with continuous stirring, and then:

- 85 g of naphthalenesulfonic acid sodium formaldehyde concentrate,

- 15 g of dioctylsulfosuccinate

- 50 g of polyvinylpyrrolidone (PVP KCO) dissolved in 175 ml of water,

- 50 g of lactose and 15 minutes after feeding the stirring of the solution is stopped. The moist powder mixture is molded to granules in a 550 mm diameter granulation vessel. The resulting product was dried in a vacuum oven at 55 ° C for approximately 2 hours to obtain a constant weight.

Example 37

Residual effectiveness against house fly (Musca domestica)

The residual activity of the products obtained according to Example 33 and Example 34 on different surfaces and against different surfaces

house fly (Musca domestica WHO / SRS) is demonstrated by the examples given below. The product, diluted with water, was sprayed onto the tiles and boards at the given doses using a Potter type sprayer. The treated surfaces were kept in the dark at 25 ° C and 50-60RH before being used. The experiment was performed in two steps using 10 -10 animals at each dose, each time using a surface that had not previously been used. The insects are exposed to the treated surfaces for 30 minutes and then transferred to clean petri dishes and fed with food containing water and sugar until they are alive. Mortality was recorded after 24 hours in the case of flies and after 48 hours in the cockroach experiment.

Values are reported as mortality rates.

The results show that the products obtained according to Example 33 and Example 34 give 100% efficiency for 15 weeks on both types of surfaces. This is twice as long as the standard Sooreh 25 WP preparation (6 weeks).

Residual efficacy of the product used against a house fly in a tile test

Product Act. in treated surface after a number of weeks Dose mg / m2 0 2 4 6 8 10 12 15 20 25 mortality in% 24 hours after 30 minutes exposure Sooreh 25 WP * 100 100 100 100 100 90 85 40 15 0 0 An example 33 25 100 100 100 100 100 100 100 100 100 100 An example 34 25 100 100 100 100 100 100 100 100 100 100

* containing permethrin as active ingredient

Residual efficacy of the product used against home fly in board testing

Product Act. in treated surface after a number of weeks Dose mg / m2 0 2 4 6 8 10 12 15 20 25 mortality in% 24 hours after 30 minutes exposure Sooreh 25 WP * 100 100 100 100 85 75 35 10 10 5 0 An example 33 50 100 100 100 100 100 100 100 100 100 100 An example 34 25 100 100 100 100 100 100 100 100 100 100

* contains permethrin as active ingredient

Residual efficacy of the product used against cockroaches (Blattella germanica) on tiles

Product Act. in treated surface after a number of weeks Dose mg / m2 0 2 4 6 8 10 12 15 20 25 mortality in% 24 hours after 30 minutes exposure Sooreh 25 WP * 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 An example 33 25 100 100 100 100 100 100 100 100 100 100

♦ contains permethrin as active ingredient ♦♦ contains cypermethrin as active ingredient ♦♦♦ contains beta-cypermethrin as active ingredient

Residual efficacy of the product used against cockroaches (Blattella germanica) on boards

Product Act. in treated surface after a number of weeks Dose mg / m2 0 2 4 6 8 10 1 2 1 5 20 25 mortality in% 24 hours after 30 minutes exposure Sooreh 25 WP * 100 100 1 00 100 80 70 40 20 5 0 0 Kordon 10WP ** 50 100 100 100 100 100 75 50 65 25 5 Chinmix 5SC *** 25 100 1 00 100 100 100 100 85 75 50 50 An example 33 25 100 100 100 100 100 100 100 100 100 100

* contains permethrin as active ingredient ** contains cypermethrin as active ingredient *** contains beta-cypermethrin as active ingredient

Example 38

Residual efficacy of the product used against cockroaches (Blattella germanica)

The residual activity of the products obtained according to Example 33 and Example 34 on different surfaces and against cockroaches (Blattella germanica) is demonstrated by the examples given below. The surfaces were treated as described in Example 37.

The results show that the products obtained according to Example 33 and Example 34 give 100% efficacy for 25 weeks when applied at a dose of 25 mg / m ² on both tiles and boards. This is twice as long as compared to Soorex 25 WP at a dose of 200 mg / m ² and compared to Kordon 10 WP at 50 mg / m ² (8 and 4, respectively, 10 and 8 weeks).

· · · · · ·

Reagents used:

TWEEN 20 - polyoxyethylene-20-sorbitan-monolaurylate

MADEOL AG / OR 95-Naphthalenesulfonic acid

PAPI 227 - polymethylene-polypropylene isocyanate

Altox - polyoxyethylene-sorbitol-hexaoleate

Wettol - phenolsulfonic acid - sodium salt

HMDA - hexamethylenediamine

ONGROMAT CR 30-20 - polymethylene-polyphenylene-isocyanate,

4,4-Diphenyl methane diisocyanate (MDI)

Claims (18)

Patent Claims A microencapsulated insecticidal product comprising 0.001 to 80% by weight as active ingredient. % 1 RcisS / 1 ScisR and / or 1 RtransS / 1 StransR isomers or isomeric mixtures of cypermethrin of formula I to a barrier material, optionally together with activity enhancers, lures, fillers and additives or mixtures thereof, coated or incorporated into single or multi-layer microcapsules of size 1 to 2000 µm according to Figures II and III, optionally prepared in the form of an insecticidal preparation together with additional insecticides and additives. A microencapsulated product according to claim 1, characterized in that it contains beta- or theta-cypermethrin as the active ingredient. A microencapsulated product according to claim 1, characterized in that it contains as a barrier material the microcapsules lignin, cellulose derivatives, starch, gelatin, resins, polyamides, polyesters, polycarbonates, polyurethanes or polycarbamide polymers. A microencapsulated product according to claim 1, characterized in that it contains insecticidal synergists, preferably piperinyl butoxide or sesame oil, as an activity enhancer. A microencapsulated product according to claim 1, characterized in that it contains as pheromones pheromones, various flavoring agents, sugars, flour, bran, finely dispersed shavings, pine resin, guaiac, lignin and preferably water or a combination thereof. A microencapsulated product according to claim 1, characterized in that it contains biologically or chemically inert substances, preferably finely dispersed cellulose, starch, limestone, silica gel powder, silicic acid, paraffin oil or mixtures thereof, as fillers. A microencapsulated product according to claim 1, characterized in that it contains, as emulsifying or suspending agents, preferably ionic or non-ionic surfactants, stabilizers and / or salts. A microencapsulated product according to claim 1, characterized in that it contains tetrametrin or aletrin as additional insecticides. 9. A method for preparing a microencapsulated insecticidal product, characterized in that a ready-to-use formulation is prepared comprising as active ingredient 1 RcisS / 1 ScisR and / or 1 RtransS / 1 StransR isomers or isomeric mixtures of cypermethrin of formula I with barrier materials, optionally together with further enhancing agents, lures, fillers and other additives and with additional insecticides, up to obtaining microcapsules of size 1 to 2000 μπι according to Figures II and III by applying coacervation and / or boundary polymerization method. Coacervation method according to claim 9, characterized in that the active substances, the enhancers, the lures, fillers and additives, as well as the material forming the barrier are mixed in an organic solvent, the mixture is stirred with water, if necessary. in the presence of surfactants, the organic solvent is evaporated or precipitated by adding to it an additional organic or inorganic coagulant or by adjusting the pH, the resulting coating barrier of the microbes obtained. the psyllium is formed to the desired strength by the addition of additional cross-linking agents, such as formaldehyde, glutaraldehyde or propylene oxide, if desired, after which the suspension is filtered and dried or converted to the desired form without filtration, in particular by the addition of additional insecticides and additives or the above processes are repeated with the suspension containing the microcapsules by adding to it additional activity enhancers, lures, fillers and additives and the multilayer material. an encapsulated substance is converted into the desired product. 11. The boundary polymerization method according to claim 9, characterized in that the active substance-enhancing agents, lures, fillers and additives, as well as the material forming the barrier or components for the material of which the barrier is formed, are mixed with solvent, the solution is dispersed in water, if desired in the presence of surfactants, then polymerization is induced on the surface of the droplets obtained by the addition of a polymerization initiating agent or by di- or polyfunctional reagent, the resulting barrier is treated to obtain the desired strength by the addition of additional crosslinking agents, such as formaldehyde, glutaraldehyde or propylene oxide, if desired, then the suspension is filtered and dried or converted to the desired form without filtering, in particular when additional insecticides and additives are added, or the processes described above are repeated with a suspension containing the microcapsules by adding additional enhancing activity to it such agents, lures, fillers and additives, and the desired product is obtained from the multilayer microencapsulated substance obtained. A method according to claims 9-11, characterized in that the microencapsulation by co-preservation and by polymerization is applied repeatedly, if desired, or in combination. 13. Method for the preparation of an insecticidal product, a batch period, characterized in that the microencapsulated product according to claim 1 is prepared in the form of a suspension concentrate, a gel suspension, a wettable powder material, a powder product, or as dispersible in water. granules. A method according to claim 13, characterized in that the suspension concentrates are prepared using water, a dispersing agent, preferably sodium ligninsulfonate, a wetting reagent, preferably an alkyl aryl polyglycol ether and a dialkyl succinate salt, antigen preferably propylene glycol or polysaccharides. 15. The method according to claim 13, wherein the gel suspension is prepared using water and a dispersing agent, preferably an epoxylatedpropoxylated block polymer and a gel-forming reagent, preferably polyacrylic acid at pH 6.5. 16. The method of claim 13, wherein the wettable powder products are prepared using a dispersing agent, preferably an alkyl salt of an aryl-aryl naphthalenesulfonic acid, a wetting reagent, for preferably polyoxyethylenealkyl ether, lubricant and filler, preferably kaolin. A method according to claim 13, characterized in that a suitable spray agent is prepared using a lubricant and a filler, preferably talc and silicic acid. 18. The method of claim 13, wherein the water-dispersible granules are prepared using conventional wet granulation and drying methods, preferably using an alkylaryl sulfonic acid-sodium salt-formaldehyde concentrate such as a dispersant, preferably a dialkyl sulfosuccinate as a wetting reagent, and preferably a polyvinylpyrrolidone and lactose as a binder and adhesive.