KR19990066935A - Microencapsulated Insecticides and Methods of Making the Same - Google Patents

Abstract

The present invention provides 0.001-80% by weight of 1R cisS / 1S cisR and / or 1RtransS / 1StransR isomers or mixtures thereof and wall materials of cypermethrin of formula (1) as an active ingredient, and, optionally, Further active enhancers, attractants, fillers and auxiliaries or mixtures thereof, embedded or enclosed in single or multiple microcapsules of 1 to 2000 μm in size according to FIG. 2 or 3, optionally further pesticides and auxiliaries A microencapsulated pesticide product formulated in a pesticide product with:

Formula (1)

Description

Microencapsulated Insecticides and Methods of Making the Same

Technical field

The present invention relates to a microencapsulated insecticide containing, as an active ingredient, an isomer of Cypermethrin of Formula (1) in a predetermined ratio, and also to a formulated product containing a microencapsulated insecticide and their Relates to a manufacturing method:

Background technology

Cypermethrin is a mixture of eight optical isomers because it is a molecule containing three asymmetric centers. In accordance with the nomenclature established by Michael Elliot, below we will characterize the arrangement of asymmetric carbon atoms encoded by α, and for R and S, the "cis" and "trans" notations, respectively, It shows the three-dimensional arrangement of the substituent of a cyclopropane ring. We have shown the arrangement of the first carbon atoms of the cyclopropane ring in the arrangement of 1R or 1S. Thus, the 1R cis isomer is 2,2-dimethyl- (2 ', 2'-dichlorovinyl) -1 (R) -cis-cyclopropane carboxylic acid-α (S) -cyano-m-phenoxy- Corresponds to benzyl-ester.

Cypermethrines characterized by formula (1) are well known pesticides containing eight possible isomers of the molecule [Ref. Pest. Man. X. Ed., 178, (1994)]. Its effectiveness can be made more selective by omitting inactive isomers, respectively. Alpha-, beta-, zeta-cypermethrin [Ref. Pest. Man. X. Ed., 179, 180, 181, (1994), and theta-cypermethrin (see, for example, Hungarian specification 198,373) were developed on this basis. The products listed below are preparations of commercially available active ingredients containing isomers:

Alpha-cypermethrin = 1R cisR / 1S cisR (1: 1)

Beta-cypermethrin = 1R cis S / 1S cis R: 1R trans S / 1S trans R (1: 1 ≡ 4/6)

Theta-cypermethrin = 1RtransS / 1StransR (1: 1)

Zeta-cypermethrin = 1R cis-trans S / 1S cis-trans S (cis / trans ≡ 4/6)

During application of the product, it was demonstrated that significant skin irritation occurred mainly by cis isomers. [Reference: Aldbridge W.N .: An assessment of the toxicological properties of pyrethroids and their neurotoxicity, In: Critical Reviews in Environmental Control Vol. 22, Issue 2, pp 89-104 (1992). This effect is greatest with alpha-cypermethrin and weakest with theta-cypermethrin. Rash, individually allergic reactions of different intensity, was observed to be severe in people in contact with the use of the product, and in more severe cases shock-like symptoms such as fever, bulging of the cheeks were involved. These symptoms occurred more seriously in people who used the product professionally. Long-term exposure to, for example, insect repellents, especially in nearby places, caused prolonged or short-term irritation symptoms. Biological studies have shown that cipermethrin and similar ferredoids are not allergens by themselves, but significantly increase the effects of other allergens and make them sensitive. These side effects limit their use and require special care when used.

Another important problem of molecules is that they are very effective against cold hematomas because they have a broad antimicrobial spectrum, but they kill too many useful organisms such as bees, natural insects, ticks, etc., regardless of the form of application, so their selection in the form of conventional products. The general application would not be safe. [Reference: Hill, R .; Effect on non-target organisms in terrestrial and aquatic environment, In: The Pyrethroid Insecticides, Ed. Leahey J. P., pp 151-262 (1985) Taylor and Francis, London.

The situation is further exacerbated by the horror effect of a significant amount of repellent, ie, pyrethroids, including cypermethrin, and cannot be used directly or with only minor efficacy against the hiding pests.

For the safe handling of hazardous substances, for example highly toxic substances, explosive processes have been developed over the last few decades based on colloidal chemistry results under the generic name of microencapsulation [Bungenberg de Jong H D, In. Colloid Sci, Ed. H. R. Kruyt; Elsevier, Amsterdam, Vol. 2, p. 249- (1949); J.R. Nixon, ed., Microencapsulation, Marcel Dekker, Inc., New York (1976); T. Kondo, ed., Microencapsulation, Techno Inc., Tokyo, Japan (1979). This is because new phases are formed on the surface of the colloidal granules or droplets, and similar materials are packed, thereby obtaining a material with new properties. This method can be carried out in a liquid or vapor phase, in solution or melt, and can occur chemically by physically interfacial polymerization reaction by phase separation coacervation. The enclosing wall formed can be solid or semisolid. The size of the granules may range from 0.1-0.2 μm to mm, the shape of which may be irregular in sphere. The active ingredient may be irregularly inserted into the granules, may have matrix properties, or may be regularly surrounded by the surrounding material. These parameters depend on the desired goals of the technology-engineering applied in large scale measurements from the physico-chemical and colloidal-fluidic properties of the applied system. The general method follows this microencapsulation and must be specifically studied and developed under the given conditions. For this reason, microencapsulation processes have been developed individually for pesticides based on different active ingredients, among others, phosphate esters. Controlled Release Pesticides, ACS Symp. Series, No 53, Am. Chem. Soc. Washington, D. C., (1977).

In the case of pyredoids containing isomers which can be isomerized in the presence of a base (eg β-cypermethrin to α-cypermethrin (HU 210,098)), microencapsulation is very difficult. This is because so far no suitable process has been performed for such products.

Detailed description of the invention

The present invention relates to microencapsulation of isomeric mixtures of cypermethrin (among them alpha and beta cypermethrins) with optimized composition and to novel products thus obtained, which protect against plants, crops and trees. It may be advantageously used in veterinary treatments, such as ektoparasiticum, in public hygiene and in the control of "home pests" such as mosquitoes, flies, cockroaches, ants, teeth, termites and the like. Disadvantages and problems characteristic of cypermethrin have been known for a long time and have been theoretically solved by microencapsulation, but the development of the desired product of the present invention is due to the individual properties of microencapsulation depending on the active ingredient. It has not been achieved until the present filing. Microencapsulated products containing selected isomers of cypermethrin have not been previously known.

In the product obtained by the process according to the invention, all non-preferred features which can be attributed to the contact activity of the cipermethrin isomers are selected from mixtures of isomers (e.g. beta and theta cypermethrin) from efficacy and innocuous aspects. By reducing or stopping. These embodiments include, but are not limited to, reducing the toxicity imposed on warm-blooded and natural aquatic organisms, and the direct contact efficacy of products within the scope of protection of the present invention is limited to useful Articulata, In addition, so long as it imposes oral toxic effects on pest breeding on treated plants, reduces exposure and its effects on humans during use, and improves selectivity in plant protection applications. Since the intake of the lethal dose is increased by reducing the repellent effect of the pyredoids, they may be preferred in embodiments that develop resistance to pests. Because of the controlled release of these active ingredients, the products according to the invention have increased sustained activity, which is of all important for professional pest control and public health. The formulations according to the invention show another advantage as long as they are water based and flammable organic solvents are regularly used in the formulation of pyredoids and are characterized by high inhalation toxicity or in powder form.

Enclosing the active ingredient enabled staff to be explicitly sensitive to ciphermethrin in advance and applied directly to the new product. The severe toxicity measured in warm-blooded organisms was excessively reduced; For microencapsulated products containing 25% beta-cypermethrin, the severe LD ₅₀ value (oral administration) for rats was> 5000 mg / kg, whereas the controlChinmix 5SC (5% beta-cysteine) Water-soluble microsuspensions containing permethrin) had an LD ₅₀ value of 1513.6 mg / kg.

An important advantage is that the process according to the invention introduces materials which are not applicable or cumbersome by conventional methods and whose co-existence in the formulation could not be solved because of their different physical and chemical properties. By this method, attractants, fillers and activity enhancers, in particular cases other pesticides and other auxiliaries, can be applied optionally. Various microencapsulations are possible by repeating the microencapsulation process and introducing these materials in a preferred process. In this way, the active ingredient can be coated with an external attractant envelope, and a product can be produced that exterminates only the species of the indicated species or hiding pests.

Since the detergent used to form the colloidal solution can be used as the surfactant applied in the final product, the microencapsulation process can also be carried out in one way and the resulting microcapsule suspension is preferably combined with another adjuvant The product should be provided without separation.

During the development of the process of the present invention, one of the objectives of the present invention is the use of halogenated solvents without restricting the scope of protection of the present invention to those methods in which an alternative method of applying ethyl acetate or petrol ether was performed. To avoid. Large scale manufacturing is possible taking into account environmental protection.

Based on the above content, this invention

0.001-80% by weight of 1R cisS / 1S cisR and / or 1RtransS / 1StransR isomers or mixtures and wall materials thereof, and optionally, FIG. 2 or FIG. Further active enhancers, attractants, fillers and adjuvants or mixtures thereof, embedded or enclosed in single or multiple microcapsules of size 1 to 2000 μm according to 3, formulated into pesticides with further pesticides and auxiliaries To microencapsulated pesticides.

Microencapsulated preparations according to the present invention include beta or theta cypermethrin as an active ingredient; Lignin, cellulose derivatives, starch, gelatin, resins, polyamides, polyesters, polycarbonates, polyurethanes, polyurea polymers as wall materials; Insecticidal agents, preferably piperonylbutoxide or sesame oil as activity enhancers; Pheromones and other attractants; Various essential oils; As fillers sugar, wheat flour, bran, finely dispersed sawdust, rosin, earcalls, lignin and preferably water or combinations thereof, biologically and chemically inert substances such as finely dispersed cellulose, starch , Limestone, silica gel powder, silicic acid, paraffin oil or mixtures thereof; Emulsifiers and suspending agents as auxiliaries, for example stabilizers and / or salts, respectively, of ionic or nonionic tensides; pyredoids such as tetramethrin, alletrin and, if desired, as additional pesticides. It contains additional adjuvants.

The invention also applies, in particular, to coacervation and / or interfacial polymerization methods, as the active ingredient 1RcisS / 1ScisR and / or 1RtransS / 1StransR isomers or mixtures thereof and wall materials of formula (1). And, if desired, further active enhancers, attractants, fillers and other auxiliaries, together with additional pesticides, in microcapsules of 1 to 2000 μm in size according to FIG. 2 or 3. It relates to a process for producing the product. According to the coacervation method of the invention, the active ingredient, the active enhancer, the attractant, the filler and the adjuvant, more particularly the wall material, is mixed with the organic solvent and the mixture is stirred with water, if necessary water with detergent And evaporate the organic solvent, precipitate by adding another organic or inorganic coagulant, or adjust the pH, and if necessary, the wall of the obtained microcapsules is further reticulated such as formaldehyde, glutaraldehyde or propylene oxide. (netting agent) is added to form the desired strength, and then the suspension is formulated without filtration by filtration and drying or by optionally adding additional pesticides and auxiliaries in the desired form, or else the process is further carried out as described above. Microcapsules containing suspension with the addition of active enhancers, attractants, fillers and auxiliaries The repetition performed by a desired product from a variety of microencapsulated materials are formulated as described above.

According to the interfacial polymerization process of the present invention, the active ingredient, active enhancer, attractant, filler and auxiliaries, more particularly the components of the wall material or wall material are mixed with an organic solvent and the solution is water, optionally water with a detergent present. Dispersed in, followed by polymerization or polycondensation by the addition of a polymerization initiator or a bifunctional or polyfunctional reagent on the surface of the formed droplets, the walls of which are formed, if necessary, such as formaldehyde, glutaraldehyde or propylene oxide. The additional strength is formed to the desired strength by addition of the netting agent, and the suspension is then filtered and dried or formulated without filtration by optionally adding additional pesticides and auxiliaries in the desired form, or else the process may be further carried out as described above. The suspension may be added by adding active enhancers, attractants, fillers and auxiliaries. Is carried out repeatedly on the microcapsules oil, the desired product from a variety of microencapsulated materials are formulated as described above.

Microencapsulation by coacervation and interfacial polymerization can be applied repeatedly, if necessary, intermittently or together.

The present invention more particularly relates to a process for the preparation of the pesticide product, characterized in that the microencapsulated product is formulated in the form of a suspension concentrate, gel suspension, wettable powder dusting agent or granules which can be dispersed in water.

Suspension concentrates are water, dispersants, preferably sodium-lignin-sulfonates, wetting agents, preferably alkyl-aryl-polyglycol ethers and dialkyl-succinate salts, antigelatines, preferably propylene glycol and polysaccharides Prepared by using; Gel suspensions are prepared by using water and a dispersant at pH = 6.5, preferably ethoxylated-propoxylated block polymers and gelatinizing agents, preferably polyacrylic acid; Wettable powder products are prepared by using dispersants, preferably alkyl-aryl-naphthalene-sulfonic and sodium salts, wetting agents, preferably polyoxyethylene-alkyl ethers, sliding agents and fillers, preferably kaolin Become; Dusting products can be prepared by using slidating agents and fillers, preferably talc and silicic acid.

The water dispersible granules are prepared from the microencapsulated product according to the present invention by conventional wet granulation and drying methods, preferably by using alkyl-aryl-sulfonic acid-sodium salt-formaldehyde condensates as dispersants; It can be prepared by using dialkyl-sulfosuccinate as the wetting agent and adhesives, preferably polyvinyl-pyrrolidone and lactose as binders.

The scope of the invention is illustrated by the non-limiting examples.

Example

Example 1

1400 g of distilled water and 1.5 g of sodium-lauryl sulfate were added to a 2 L beaker fed with the mixture. The solution was mixed at 1200 r / m. 60 g of beta-cypermethrin and 30 g of ethyl cellulose ("Hercules" N-200, 154 cP) were dissolved in 463 g of dichloromethane and the solution was poured into an aqueous solution. The reaction mixture was stirred at rt for 8 h, then the formed microcapsules were left to stand, poured along the green solution, washed with water, filtered and dried under an infrastructure lamp. A white powdery product was obtained, which yielded 57.64 g. The average size of the granules was 135 μm and the assay rate was 64%.

Example 2

The same procedure as in Example 1 was conducted except that 354 g of chloroform was used instead of dichloromethane. A white powdery product was obtained, which yielded 57 g. The average size of the granules was 207 μm and the assay rate was 54.2%.

Example 3

The same procedure as in Example 1 was conducted except that 315 g of ethyl acetate was used instead of dichloromethane. A white powdery product was obtained, which yielded 55.4 g. The average size of the granules was 241 μm and the assay rate was 66%.

Example 4

The same procedure as in Example 1 was conducted except that the product was dried in open air instead of using an infrastructure ramp. A white powdery product was obtained, which yielded 75 g. The average size of the granules was 267 μm and the assay rate was 40%.

Example 5

It was carried out in the same manner as in Example 4 except that 20% by weight of sugar was dissolved in distilled water as a attractant additive before microencapsulation and the process was performed with this solution. A white powdery product was obtained, which yielded 77.2 g. The average size of the granules was 254 μm and the assay rate was 9.2%. Sugar content: 7.7%. Water content: 35.2%.

Example 6

50 g of beta-cypermethrin was used instead of 60 g and was carried out in the same manner as in Example 1 except that 10 g of piperonylbutoxide (PBO) was used as a synergist. A white powdery product was obtained, which yielded 56.2 g. The average size of the granules was 237 μm and the assay rate was 45.3%. PBO content: 18%.

Example 7

The same procedure as in Example 6 was conducted except that sesame oil was used instead of PBO as a synergist. A white powdery product was obtained, which yielded 57 g. The average size of the granules was 75.6 μm and assay rate was 44%. Sesame oil content: 19%.

Example 8

To a 1 L beaker fed with the mixture was added 700 g of distilled water and 1.2 g of sodium-lauryl sulfate. The resulting solution was mixed at 1200 r / m. 15 g of theta-cypermethrin and 30 g of ethyl cellulose (“Hercules” N-200, 154 cP) were dissolved in 175 g of dichloromethane and the solution was poured into an aqueous solution. The reaction mixture was stirred at rt for 8 h, then the formed microcapsules were left to stand, poured along the green solution, washed with water, filtered and dried under an infrastructure lamp. The product in the form of a white powder was obtained, which yielded 27.4 g. The average size of the granules was 132 μm and the assay rate was 50.8%.

Example 9

The same procedure as in Example 8 was carried out except that 30 g of ethyl cellulose was used instead of 15 g of ethyl cellulose. White powder-like product was obtained, which yielded 41 g. The average size of the granules was 239 μm and the assay rate was 32%.

Example 10

The procedure was the same as in Example 8 except that 25 g of ethyl cellulose instead of 15 g and 0.25 g of theta-cypermethrin were used instead of 15 g. White powder-like product was obtained, which yielded 27.2 g. The average size of the granules was 118 μm and the assay rate was 1%.

Example 11

5 g of theta-cypermethrin was used instead of 15 g, and the same procedure as in Example 8 was conducted except that 10 g of paraffin oil was used as a filler. A white powder like product was obtained, which yielded 26.2 g. The average size of the granules was 123 μm and the assay rate was 14.1%. Paraffin oil content: 31%.

Example 12

Into a 250 ml beaker provided with a stirrer was added 2.5 g of polyvinyl alcohol (PVA) (Merck, Mr about 72000), 57.5 g of distilled water and 0.05 g of sodium-lauryl-sulfate. The mixture was stirred at 1200 r / min. 4 g of beta-cypermethrin was dissolved in 5.5 g of xylene and the solution was poured into an aqueous solution. The resulting mixture was stirred at room temperature for 10 minutes and then 36 ml of 20% sodium sulfate solution was added dropwise. After stirring for 15 minutes, the pH was adjusted to 3.4-4 with citric acid, then the walls of the formed microcapsules were cured with 2 ml of formaldehyde while stirring one more, the product was left, poured along the top solution and washed with water. Filtered, dried in air. A white powder like product was obtained, yielding 8.2 g. The average size of the granules was 243 μm and the assay rate was 42%.

Example 13

The same procedure as in Example 12 was carried out except that 5.5 g of aromatol was used instead of xylene. A white powder like product was obtained, which yielded 8.7 g. The average size of the granules was 250 μm and the assay rate was 37.2%.

Example 14

The same procedure as in Example 12 was carried out except that 2.5 g of hydroxypropyl-methyl cellulose was used instead of polyvinyl alcohol (PVA). White powder-like product was obtained, which yielded 7.6 g. The average size of the granules was 217 μm and the assay rate was 33%.

Example 15

The same procedure as in Example 12 was carried out except that 2.5 g of cellulose-acetate-phthalate was used instead of polyvinyl alcohol. A white powder like product was obtained, which yielded 7.9 g. The average size of the granules was 203 μm and assay rate was 37%.

Example 16

A large amount of 60 g of carbamide, 86 g of formaldehyde solution and 10% aqueous ethanolamine solution was added in a device provided with a magnetic stirrer to bring the pH of the resulting mixture to 7.5. The frying mixture was warmed to 70 ° C. with stirring and left at this temperature for 2 hours. 9.5 g of the water-soluble carbamide-formaldehyde polymer complex formed were dissolved in 160 g of distilled water, and 0.1 g of Tween-20 detergent was added to the solution. 4 g of beta-cypermethrin was dissolved in 5.5 ml of xylene with stirring at 1200 r / min and added to the solution. After stirring for 10 minutes, the mixture was added to an aqueous citric acid solution and the pH of the mixture was adjusted to 3.5-4 by dropwise addition of 100 g sodium sulfate in a 25 $% solution. Then, to reinforce the walls of the microcapsules, 3 ml of formaldehyde solution was added and stirred for 1 hour. Poured along the top solution of the product, washed with water, filtered and dried. White powder-like product was obtained, yielding 21 g. The average size of the granules was 168 μm and the assay rate was 17.2%.

Example 17

The same procedure as in Example 16 was carried out except that 1 g of glutaraldehyde was used instead of formaldehyde. A white powder like product was obtained, yielding 19.8 g. The average size of the granules was 168 μm and the assay rate was 16.9%.

Example 18

40 g of 0.5% PVA solution and 4 g of Dispergens A detergent were added into a 100 ml beaker provided with a Turax mixer. After stirring at 3800 r / m, 4 g of beta-cypermethrin solution, 1.8 g of diphenyl-methane-diisocyanate dissolved in 8 g of xylol was added and stirred for 5 minutes. A 40% aqueous solution of 1.4 g of hexamethylene-diamine was added to the mixture, and the mixture was stabilized with 1 g of polyethylene glycol after stirring of water. The pH of the mixture was adjusted to 5 to 5.5 with 33% formic acid solution. The product obtained is used directly. Average size of granules: 4.8 μm.

Example 19

The same procedure as in Example 18 was carried out except that ONGRONAT CR 30-20 was used instead of diphenyl-methane-isocyanate. Average granule size: 8.0 μm.

Example 20

16.5 g of distilled water and 0.67 g of MACEOL OR / 95 BA detergent were added to a 50 ml beaker provided with a Turax mixer. After stirring at 8000 r / m, the solution was cooled to 5 ° C. After dissolving 4.26 g of beta-cypermethrin and 1.03 g of PAPI227 in 8.51 g of aromatol, the solution was poured into an aqueous solution. After the obtained mixture was stirred for 6 minutes, 1.43 ml of 43.2% hexamethylene-diamine solution was added dropwise to the mixture. After further stirring for 3 minutes, the pH of the mixture was adjusted to 5-5.5 with 33% formic acid solution. The product obtained is used directly. Average size of granules: 1.4 μm.

Example 21

The same procedure as in Example 20 was carried out except that 1.03 ml of 42% diethylene-triamine solution was used instead of the hexamethylene-diamine solution. Average granule size: 4.4 μm.

Example 22

The same procedure as in Example 20 was carried out except that 2.06 ml of an aqueous 11% 2,5-dimethyl-2,5-hexanediol solution was used instead of the hexamethylene-diamine solution. Average size of granules: 2.6 μm.

Example 23

The same procedure as in Example 20 was carried out except that 2.06 ml of an aqueous 42.3% malonic acid solution was used instead of the hexamethylene-diamine solution. Average size of granules: 2.8 μm.

Example 24

0.6 ml of triethanolamine was used instead of the hexamethylene-diamine solution, and the same procedure as in Example 20 was carried out except that 0.75 g of a PBO synergizing substance was added to the active ingredient. Average size of granules: 2.3 μm.

Example 25

The same procedure as in Example 20 was carried out except that Atrox was used as a detergent. Average size of granules: 1.5 μm.

Example 26

25 ml of a 25 ml 0.5% PVA solution provided with a Turax mixer and 0.1 g of Wetol detergent were added. The temperature was cooled to 5 ° C. while the solution was stirred at 8000 r / m. After 2 g of beta-cypermethrin and 2 g of sebacic acid chloride were dissolved in 3 g of xylene, the solution was poured into an aqueous solution. After the obtained mixture was stirred for 6 minutes, a solution prepared by dissolving 0.75 g of ethylenediamine and 1.2 g of diethylenediamine in 10 ml of water was added dropwise. The product used directly was stabilized in the final reaction by adding 5 ml of 25% sodium sulfate solution. Average size of granules: 5.7 μm.

Example 27

The same procedure as in Example 22 was carried out except that 2 g of 2,4-toluene-diisocyanate and 0.36 g of MADEOL were used as the detergent instead of sebacic acid chloride. Average size of granules: 4.6 μm.

Example 28

The same procedure as in Example 22 was carried out except that kerosene was used instead of xylene as a solvent. Average size of granules: 3.5 μm.

Example 29

After adding 20 ml of distilled water and 0.4 g of Wetol in a beaker provided with a stirrer, the obtained solution was mixed at 1200 r / m. After 4 g of beta-cypermethrin and 0.4 g of PAPI were dissolved in 4 ml of xylene, the solution was added to the aqueous solution. After stirring for 15 minutes, 2 ml of 42.3% aqueous HMDA solution was added. After stirring for 5 minutes, the pH of the mixture was adjusted to 5-5.5 with 33% formic acid solution. The supernatant of the obtained product was poured along, washed with water, filtered and dried. White powder-like product was obtained, which yielded 4.2 g. Assay rate: 44%. Average size of granules: 67 μm.

Example 30

The procedure was the same as in Example 29 except that 150 ml of 0.5% PVA solution as the aqueous phase and 6 g of sebacic acid chloride dissolved in 38 g of beta-cypermethrin and 38 g of dichloromethane were used as the organic phase. The walls of the capsules were developed by applying 6 ml of 42.3% HMDA solution. White powder-like product was obtained, which yielded 14 g. Average size of granules: 73 μm. Assay rate: 31%.

Example 31

The same procedure as in Example 29 was conducted except that 150 ml of 0.5% starch solution was used as the protective colloid. A white powder like product was obtained, yielding 12.7 g. Average size of granules: 85 μm. Assay rate: 29%.

Example 32

Preparation of Gel

To 1500 g of the product prepared according to Example 1, 1300 g of water and 100 g of naphthalene sulfonic acid formaldehyde sodium salt were added, stirred for 3 minutes, and then to the resulting suspension, propylene oxide-ethylene oxide by-product (Pluronic) P65, BASF) 30g was added. After stirring for 2 minutes, 30 g of polyacrylic acid (Carbopol 940) was added to the mixture, and then the pH was adjusted to 6.5 by applying 1N NaOH solution.

Example 33

Preparation of Suspension Concentrate (FW)

To 900 g of the product prepared according to Example 8 was added 900 g of water and 38 g of sodium lignin sulfonate under the mixing conditions of Example 30.

Then, while stirring for 5 minutes

15 g of nonylphenol-polyglycol ether (EO = 10)

10 g of dioctyl-sulfosuccinate sodium salt

7 g of propylene glycol and

32 g of aqueous 2% xanthan rubber solution were added continuously. The xant rubber was added and stirred vigorously for 5 minutes.

Example 34

Preparation of Wettable Powder Product (WP)

In 500 g capsules prepared according to Example 16, continuously stirring in a Lodige mixer with a working volume of 5 L, 55 g of alkyl-naphthalene sulfonic acid sodium salt, 35 g of polyoxyethylene alkyl ether, synthetic silicic acid (Aerosil ) 300) and 395 g of kaolin were added sequentially. Homogenization was continued for 5 minutes.

Example 35

Preparation of Dusting Powder (P)

With continuous stirring in a 5 liter working volume in a lodge mixer, 300 g of talc, 275 g of silicic acid (Wessalon) and 25 g of synthetic silicic acid (Aerosil 200) were added to 500 g of the product prepared according to Example 29. It was added continuously. Continue mixing for 5 minutes.

Example 36

Preparation of Water Dispersible Granules (DG)

850 g of the product prepared according to Example 16 was added into a lodge mixer with a working volume of 5 L with continuous stirring.

-Naphthalene Sulfonate Sodium Salt Formaldehyde Concentrate 85g

-15 g of dioctyl sulfosuccinate

50 g of polyvinyl-pyrrolidone (PVP K30) dissolved in 175 ml of water

50 g of lactose were added continuously.

Stirring was stopped 15 minutes after the solution was fed. The wettable powder mixture was formulated into granules in a pan granulation apparatus with a diameter of 550 mm. The product obtained was dried in a vacuum drying oven at 55 ° C. for about 2 hours to give a constant weight.

Example 37

Residual Efficacy on Housefly

The residual potency of the products prepared according to Examples 33 and 34 on different surfaces and for houseflies (housefly WHO / SRS) was demonstrated by the following examples. The product diluted with water was sprayed at the doses indicated on the tiles and planks with the aid of a porter spraying tower. The treated surfaces were stored at 25 ° C. and 50-60 RH in the dark until they were used. The test was repeated twice using 10-10 animals at each dose each hour on a surface that was not previously used. After insects were exposed to the treated surface for 30 minutes, they were placed in clear Petri dishes and fed with water and, optionally, food consisting of sugar. Mortality was assessed after 24 hours for flies and 48 hours after cockroaches. The value is expressed as percent mortality. The results show that the products prepared according to Examples 33 and 34 provide 100% efficacy for 15 weeks on both types of surfaces. This represents twice the cougar against the standard Coopex 25 WP (6 weeks).

Residual Efficacy of Products Tested for Housefly on Tiles

product Active ingredient Surface time treated (Note) Capacity (mg / m ² ) 0 2 4 6 8 10 12 15 20 25 Percent mortality rate 24 hours after 30 minutes of exposure Coopex 25WP * 100 100 100 100 100 90 85 40 15 0 0 Example 33 25 100 100 100 100 100 100 100 100 100 100 Example 34 25 100 100 100 100 100 100 100 100 100 100 * Contains Permethrin as an active ingredient.

Residual Efficacy of Products Tested for Housefly on Board

product Active ingredient Surface time treated (Note) Capacity (mg / m ² ) 0 2 4 6 8 10 12 15 20 25 Percent mortality rate 24 hours after 30 minutes of exposure Coopex 25WP * 100 100 100 100 85 75 35 10 10 5 0 Example 33 50 100 100 100 100 100 100 100 100 100 100 Example 34 25 100 100 100 100 100 100 100 100 100 100 * Contains permethrin as an active ingredient.

Residual Efficacy of Products Tested for Cockroaches on Tiles

product Active ingredient Surface time treated (Note) Capacity (mg / m ² ) 0 2 4 6 8 10 12 15 20 25 Percent mortality rate 24 hours after 30 minutes of exposure Coopex 25WP * 200 100 100 100 100 100 75 60 30 0 0 Kordon 10WP ** 50 100 100 100 100 100 100 95 90 85 40 Chinmix 5SC *** 25 100 100 100 100 100 100 100 100 90 65 Example 33 25 100 100 100 100 100 100 100 100 100 100 * Contains permethrin as an active ingredient. ** contains cypermethrin as an active ingredient. *** contains beta-cypermethrin as an active ingredient.

Residual Efficacy of Products Tested for Cockroaches on Planks

product Active ingredient Surface time treated (Note) Capacity (mg / m ² ) 0 2 4 6 8 10 12 15 20 25 Percent mortality rate 24 hours after 30 minutes of exposure Cupex 25WP * 100 100 100 100 80 70 40 20 5 0 0 Codon 10WP ** 50 100 100 100 100 100 75 50 65 25 5 Chinmix 5SC *** 25 100 100 100 100 100 100 85 75 50 50 Example 33 25 100 100 100 100 100 100 100 100 100 100 * Contains permethrin as an active ingredient. ** contains cypermethrin as an active ingredient. *** contains beta-cypermethrin as an active ingredient.

Example 38

Residual Efficacy on Cockroaches

The residual efficacy of the products prepared according to Examples 33 and 34 was demonstrated on different surfaces and for cockroaches by way of example below. The surface was treated as described in Example 37. The product prepared according to Examples 33 and 34 showed 100% efficacy over 25 weeks when applied at 25 mg / m ² on tiles and planks. This represents a double cougar of codon 10 WP (8 and 4 10 and 8 weeks respectively) efficacy at Copex 25 WP and 50 mg / m ² doses at 200 mg / m ² dose.

Reagents Used:

TWEEN 20-polyoxyethylene-20-sorbitan-monolaurylate

MADEOL AG / OR 95-naphthalene-sulfonic acid

PAPI 227-Polymethylene-Polyphenylene-Isocyanate

Atrox-polyoxyethylene-sorbitol-hexaoleate

Wetol-Phenol Sulfonic Acid-Sodium Salt

HMDA-hexamethylenediamine

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

4,4-diphenyl-methane-diisocyanate (MDI)

Claims (18)

0.001-80% by weight of 1R cisS / 1S cisR and / or 1RtransS / 1StransR isomers or mixtures thereof and wall materials of cypermethrin of formula (1) as an active ingredient, and optionally in FIGS. 2 or 3 Thus it comprises additional active enhancers, attractants, fillers and adjuvants or mixtures thereof, embedded or enclosed in single or multiple microcapsules of 1 to 2000 μm in size, optionally formulated into the pesticide product together with further pesticides and auxiliaries. Microencapsulated Pesticide Products: Formula (1) The microencapsulated product according to claim 1, which contains beta-cypermethrin or theta-cypermethrin as an active ingredient. The microencapsulated product of claim 1, further comprising microcapsule lignin, cellulose derivatives, starch, gelatin, resins, polyamides, polyesters, polycarbonates, polyurethanes, or polyurea polymers as wall material. 2. The microencapsulated product according to claim 1, which contains an insecticidal agent, preferably piperonylbutoxide or sesame oil as an activity enhancer. The method of claim 1, wherein the microencapsulated containing pheromone, different odorants, sugar, wheat flour, bran, finely dispersed sawdust, rosin, earcalls, lignin and preferably water or a combination thereof as an attractant. product. 2. The microencapsulated product according to claim 1, which contains as filler a biologically and chemically inert material, preferably dispersed cellulose, starch, limestone, silica powder, silicic acid, paraffin oil or mixtures thereof. 2. Microencapsulated product according to claim 1, which contains emulsifiers and suspending agents, preferably ionic or nonionic tensides, stabilizers and / or salts as adjuvants. The microencapsulated product according to claim 1, which contains tetramethrin or alletrin as further insecticide. 1R cisS / 1ScisR and / or 1RtransS / 1StransR isomers or mixtures thereof and wall materials of cypermethrin of formula (1) as an active ingredient by applying coacervation and / or interfacial polymerization method, and Optionally, a method of making a microencapsulated pesticide product comprising formulating additional active enhancers, attractants, fillers and other auxiliaries and additional pesticides into microcapsules having a size of 1 to 2000 μm according to FIG. 2 or 3. . Mixing an active ingredient, an active enhancer, an attractant, a filler, an adjuvant and a wall material with an organic solvent; Mixing the obtained mixture with water, if desired, water in the presence of a detergent; Evaporating the organic solvent, adding additional organic or inorganic coagulants or adjusting the pH to precipitate the mixture; If desired, adding additional networking agents such as formaldehyde, glutaraldehyde or propylene oxide to form to a desired extent the walls of the resulting microcapsules; And The suspension is filtered to dry or, optionally, converted to the product without filtration by the addition of additional pesticides and auxiliaries, or the process is repeated with microcapsules containing the suspension with the addition of additional active enhancers, attractants, fillers and auxiliaries. The process of coacervation according to claim 9 comprising converting the various substances into products. Mixing the active ingredient, active enhancer, attractant, filler, adjuvant and components of the wall material or wall material with an organic solvent; Dispersing the solution in water, if desired, in water with detergent; Adding a polymerization initiator or a bifunctional or multifunctional reagent to cause polymerization on the surface of the formed droplets; If desired, adding additional networking agents such as formaldehyde, glutaraldehyde or propylene oxide to develop the formed walls to the desired strength; And The suspension is filtered to dry or, optionally, converted to the product without filtration by the addition of additional pesticides and auxiliaries, or the process is repeated with microcapsules containing the suspension with the addition of additional active enhancers, attractants, fillers and auxiliaries. 10. The process of claim 9 comprising converting the various materials into products. 12. The method of any one of claims 9 to 11, wherein the coacervation and interfacial polymerization microencapsulation are repeated several times, if desired, intermittently or together. A method of making a pesticide product comprising formulating the microencapsulated product of claim 1 in suspension concentrate, gel suspension, wettable powder product, dusting product, or water dispersible granules. The method of claim 13, further comprising: water; Dispersants, preferably sodium lignin sulfonate; Wetting agents, preferably alkyl-aryl-polyglycolethers, dialkyl-succinate salts; A process comprising preparing a suspension concentrate using an antigelling agent, preferably propylene glycol or polysaccharides. The method of claim 13, further comprising: water at pH = 6.5; A process comprising preparing a gel suspension using a dispersant, preferably an ethoxylated-propoxylated block polymer and a gel former, preferably polyacrylic acid. 14. A dispersant according to claim 13, preferably an alkyl-aryl-naphthalene-sulfonic acid sodium salt; Wetting agents, preferably polyoxyethylene-alkyl ethers; A process comprising preparing a wettable powder product using a slidating agent and a filler, preferably kaolin. The process according to claim 13 comprising preparing a dusting product using a slidating agent, a filler, preferably talc and silicic acid. 14. A process according to claim 13, wherein the process is conventional wet granulation and drying, and dispersants are preferably alkyl-aryl-sulfonic acid-sodium salt-formaldehyde concentrates; A process comprising preparing water dispersible granules using dialkyl-sulfosuccinate as the wetting agent and preferably polyvinyl-pyrrolidone and lactose as binders and adhesives.