WO1997014308A1 - Microencapsulated insecticide preparations and a process for the preparation thereof - Google Patents

Microencapsulated insecticide preparations and a process for the preparation thereof Download PDF

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WO1997014308A1
WO1997014308A1 PCT/HU1996/000060 HU9600060W WO9714308A1 WO 1997014308 A1 WO1997014308 A1 WO 1997014308A1 HU 9600060 W HU9600060 W HU 9600060W WO 9714308 A1 WO9714308 A1 WO 9714308A1
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product
preferably
microencapsulated
additional
agent
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PCT/HU1996/000060
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French (fr)
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Ildikó BAKONYVÁRI
Béla BERTÓK
László CSÍZ
Ágnes JÁNOSI
László PAP
István Székely
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Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt.
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28Microcapsules or nanocapsules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

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

Description

Microencapsulated insecticide preparations and a process for the preparation thereof

The invention relates to a microencapsulated insecticide preparation containing as active ingredient isomers of Cypermethrin of the formula I in a pre-selected ratio, fiirthermore to a formulated product containing the microencapsulated preparation and to a process for the preparation thereof. Cypermethrin is a molecule containing 3 asymmetry centres and so it is a mixture 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 , with R and S respectively " Cis " and " trans " designations are covering the steric 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 IR or I S. Accordingly the IReisS isomer corresponds to 2,2 dimethyl-( 2 ,2 - dichlorovinyl) - 1(R) -cis- cyclopropan-carboxylic acid - α(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 (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 - Cypeπnethrm = lRcisR/1 ScisR in a 1 : 1 ratio Beta - Cypermethrin = lRcisS/lScisR : lRtransS/lStransR in a 1 : 1 ≡ 4/6 ratio

Theta - Cypermethrin = IRtransS/lStransR 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 significant 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 Environmental Control Vol. 22, Issue 2, pp 89-104 (1992)). This effect is the most significant in the case of alpha- Cypermethrin and the weakest at theta- Cypermethrin. On persons using and contacting with the products eruptions, 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. Particularly longer exposition to e.g. pesticides in closed places resulted irritation symptoms 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 use requires special care.

Another significant problem of the molecule is that because of having a broad spectrum 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 selective application in the form of conventional products can not be secured. (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 worsened by the significant repellent i.e. frightening effect of the pyrethroids including Cyperaietlirin 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 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)). The point of this is that on the surface of colloid size granules or droplets a new phase is made, quasi the substance is packed in, by which 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 wall can be solid or semi-solid. The size of the granule can vary from 0,1 - 0,2 μm to the mm range, and its shape from regular globe to an irregular form. The active ingredient can be imbedded into the granule irregularly, it can have matrix character, or it can be surrounded regularly by the wrapping substance. These parameters depend in a large measure from physico-chemical and colloido- rheological characteristics of the system applied and within 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., (1977)).

In the case of pyrethroids containing isomers which can isomerize in the presence of a base (e.g. β-Cypermethrin to -Cypermethrin (HU 210.098) microencapsulation 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 microencapsulation 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 eliminated 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 containing selected isomers of Cypermetlirin 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 mixtures (e.g. beta and theta Cypermethrin) from the aspects of efficiency and haπnlessness. These aspects include but are not limited to decrease of toxicity exerted on warm- blooded and aquatic living creatures the latter living in natural waters, reducing exposition and effects on humans 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 inflammable organic solvents used regularly in the formulation of pyrethroids and characterised by high inhalation 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 containing 25 % beta- Cypermethrin the acute per os LD50 value for rats was > 5000 mg kg while in the case of the control Chinmix 5SC (aqueous micro suspension containing 5% beta- Cypermethrin) the LD50 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 cumbersome by the conventional methods, respectively their coexistence within a preparation was not solvable because of their different physical and chemical indices. By this method attractants, filling and activity enhancing materials, in particular cases further insecticides and other auxiliary 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 exterminate only the individuals of a given species or hiding pests. Because the detergents used for forming colloidal solution can be the same as the surface active agents applied in the end product the microencapsulation procedure can be carried out also in a way, that the produced microcapsule suspension should provide without isolation, preferably with further auxiliary 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 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.

On the base of the aboves our invention relates to

a microencapsulated insecticide preparation comprising as active ingredient 0.001 - 80 w % I RcisS/l ScisR and/or IRtransS/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 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.

The microencapsulated preparation according to the invention contains beta or theta Cypermethrin as active ingredient; lignin, cellulose derivatives, starch, gelatine, resin, polyamide, polyester, polycarbonate, polyurethane, polyurea polymers as wall material; insecticide synergents, preferably piperonylbutoxide or sesame oil as activity enhancer; pheromones and other attractants; various essential oils; sugars, flour, 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 auxiliary materials, e.g. ionic or non ionic tensides respectively stabilizers and/ or salts; pyrethroids e.g. tetramethrin, alletrin as additional insecticide and if desired further auxiliary materials.

Our invention relates furthermore to a process for preparing microencapsulated insecticide product characterised by formulating IRcisS/lScisR and/or IRtransS/lStransR isomers or isomer mixtures of Cypermethrin of formula I. as active ingredient with wall materials, if desired with additional activity enhancing, attractant, filling and other auxiliary materials and if desired with additional insecticides to microcapsules of 1-2000 μm 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 organic solvent is evaporated or precipitated by adding to it additional organic or inorganic coagulant, or by adjusting the pH, the wall of the 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 without filtration optionally by adding to it additional insecticides and auxiliary materials in the desired form, or the above processes are repeated with the microcapsules containing suspension by adding to it additional 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 furthermore 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 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 without filtration optionally by adding to it additional insecticides and auxiliary materials in the desired form, or the above process is repeated with the microcapsules contaming suspension by adding to it additional activity enhancers, attractants. filling and auxiliary materials as described above and from the manifold microencapsulated substance the desired product is formulated as described above.

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

Our invention relates ftirthermore to a process for the preparation of insecticide products characterised by that the microencapsulated product is formulated in the form of suspension concentrate, gel suspension, wettable powder dusting material, or as granules dispersible in water. Suspension concentrates can be prepared by using water, dispersing agent, preferably sodium-lignin-sulfonate, wetting agent, preferable alkyl-aryl-polyglycolether and dialkyl-succinate salt, antigelation agent, preferable propylenglycol and polysaccharide; gel suspensions by using water and dispersing agent, preferable ethoxylated-propoxylated block polymer and gelating agent, preferable polyacrylic acid at pH = 6,5; wettable powder products by using dispersing agent, preferable alkyl-aryl- naphthalene-sulfonic acid sodium salt, wetting agent, preferable polyoxyethylen - alkyl ether, sliding agent and filling agent, preferable kaolin; dusting product by using sliding agent and filling agent, preferable talc and silicic acid.

Granules dispersible in water can be prepared from the microencapsuleted products accordmg to the invention by usual wet granulating and drying methods, preferable using as dispersing agent alkyl-aryl-sulfonic acid-sodium salt-formaldehyde condensate; as wetting agent dialkyl-sulfosuccinate and as binding - adhesive preferable 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 1200 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 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 μm, assay

64 %. 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 granules : 207 μm, assay 54.2 %.

3)

It is proceed as in example 1 ) with the difference that instead of dichloromethane 315 g ethyl acetate are used. The yield is 55.4 g; white powderlike product. Average size of granules : 241 μm, 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 μm, assay 40 %. Water content: 34 %.

5)

It is proceed as in example 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 μm, assay 9.2 %. 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 piperonylbutoxide ( PBO) are used. The yield is 56.2 g; white powderlike product. Average size of granules : 237 μm, assay 45.3 %. PBO content: 18 %.

7) 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 μm, assay 44 %. Sesame oil content : 19 %. 8)

Into a 1 1 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 . 15 g theta- Cypermethrin and 15 g. ethyl cellulose ( "Hercules" 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 μm, 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: 239μm, 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-Cypeimethrin are used. The yield is 27.2 g; white powderlike product. Average size of granules : 118 μm, assay 1 %.

H) It is proceed as in example 8) with the difference that instead of

15 g, 5 g theta- Cypermethrin and as filling substance 10 g paraffin oil are used. The yield is 26.2 g; white powderlike product. Average size of granules : 123 μm, assay 14,1 %. Paraffin 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 and 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 minutes at room temperature then 36 ml 20 % sodium sulfate solution is dropped to it. After stirring for 15 minutes the pH is adjusted to 3,5 - 4 with citric acid then the wall of the formed microcapsules hardened by 2 ml formaldehyde solution, for 1 more hour stirred, the product settled, decanted, washed with water, filtered and dried in air. The yield is 8.2 g; white powder. Average size of granules: 243 μm, assay 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 : 250 μm, 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 granules : 217 μm, 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 μm, assay 37 %.

16)

Into an apparatus supplied with magnetic stirrer 60 g carbamide, 86 g formaldehyde solution and 10 % aqueous ethanolamine 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 2 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 ml xylene are added to it. After 10 minutes stirring the pH of the mixture is adjusted to 3,5-4 by adding to it aqueous citric acid solution and then dropping to it 100 g sodium-sulfate in a 25 % solution. In order of strengthening the walls of microcapsules 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 μm. 17)

It is proceed as in example 16) with the difference that instead of formaldehyde 1 g glutaraldehyde is used. The yield is 19.8 g; white powderlike product. Average size of granules 168 μm, assay 16.9%.

18)

Into a 100 ml beaker supplied with Turax mixer 40 g 0,5 % 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 minutes. To the mixture a 40 % water solution of 1,4 g hexamethylene- diamine 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 % formic acid solution. The product is used directly. Average size of granules: 4,8 μm.

19) It is proceed as in example 18) with the difference that instead of diphenyl-methane-isocyanate ONGRONAT CR 30-20 is used. Average granule size: 8,0 μm.

20) Into a 50 ml beaker supplied with Turax mixer 16.5 g distilled water and 0.67 g MADEOL OR/95 Bλ detergent are added. After stirring at 8000 r/m the solution is cooled to 5°C. 4.26 g beta-Cypermethrin and 1.03 g PAPI227 are dissolved in 8.51 g aromatol then this solution is poured to the aqueous one. The mixture is stirred for 6 minutes then 1.43 ml of 43.2% hexamethylene-diamine solution are dropped to it. After stirring for 3 more minutes the pH of the mixture is adjusted to 5-5,5 by 33% formic acid solution. The product is used directly. Average size of granules : 1.4 μm.

21)

It is proceed as in example 20) with the difference that instead of hexamethylene-diamine solution 1.03 ml 42 % aqueous diethylene- triamine solution are used. Average granule size : 4.4 μm. 22)

It is proceed as in example 20) with the difference that instead of hexamethylene-diamine solution 2.06 ml of 1 1 % aqueous 2,5-dimethyl- 2, 5 -hexanediol solution are used. Average size of granules: 2.6 μm.

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 μm.

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 μm.

25) It is proceed as in example 20) with the difference that Atlox is used as detergent. Average size of granules: 1.5 μm.

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-Cypeimethrin 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 diethylenediamine in 10 ml water is dropped to it. The product which is used directly is stabilized at the end of the reaction by adding to it 5 ml 25 % sodium sulfate solution. Average size of granules: 5.7 μm.

27)

It is proceed as in example 22) 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 μm. 28)

It is proceed as in example 22) with the difference that instead of xylene kerosene is used as solvent. Average size of granules: 3.5 μm.

29)

Into a beaker supplied with stirrer 20 ml of distilled water, 0.4 g Wettol are added then the solution is mixed at 1200 r/min. 4 g beta- Cypermethrin 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 2 ml 42.3 % aqueous HMDA solution are added to it. It is stirred for 5 minutes then the pH of the mixture is adjusted to 5-5,5 by a 33 % formic 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 μm.

30)

It is proceed as in example 29) 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 μm. 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 powder. Average size of granules: 85 μm. Assay: 29 %.

32) 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 2 minutes 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. 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 2 % Xanthan gum aqueous solution are added successively, with 5 minute stirring

Intensive stirring is continued for 5 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 Lόdige mixer of 5 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 5 minutes.

35) Preparation of dusting powder ( P)

To 500 g product prepared according to example 29) while stirring it contmuously in a Lόdige mixer of 5 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 minutes.

36) Preparation of water - dispersible granules (DG) Into a Lόdige mixer of 5 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-pyτrolidone( PVP K30) dissolved in 175 ml water - 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. 37) Residual efficacy against house fly (Musca domestica)

Residual efficacy of the products prepared according to examples 33) and 34) on different surfaces and against home fly (Musca 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 25°C and 50-60 RH until using them. Tests were carried out in two repetition using 10 -10 animals in each dose every time on surfaces previously not used. The insects are exposed to the treated surfaces for 30 minutes 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. The values were expressed as percent mortality.

The results show that the products prepared according to examples 33) and 34) gave 100 % efficiency for 15 weeks on both types of surfaces. This is two times couger then the standard Coopex 25 WP (6 weeks).

Figure imgf000019_0001
jLQ *contaιns Permethπn as active ingredient

1 5

20

Figure imgf000019_0002

*contaιns Permethπn as active insredient

25

30

Figure imgf000019_0003
contains Permethπn as active ingredient contains Cypermethrin as active ingredient contains Beta - Cypermethrin as active ingredient
Figure imgf000020_0001

* contains Permethπn as active ingredient ** contains Cypermethrin as active ingredient contains Beta - Cypermethrin as active ingredient

36) Residual efficacy agamst cockroaches (Biattella germanica )

Residual efficacy of the products prepared accordmg to examples 33) and 34) is demonstrated on different surfaces and against cockroaches (Biattella germanica) 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 25 weeks when applied at 25 mg/m^ dose on tiles and on board. This is two times cuger then the efficiency of Coopex 25 WP at 200 mg/m- dose and of Kordon 10 WP at 50 mg/m- dose (8 and 4 resp. 10 and 8 weeks).

Reagents applied:

TWEEN 20- polyoxyethylene- 20- sorbitane - monolaurylate MADEOL AG/OR 95 - naphthalene - sulfonic acid PAPI 227 - polymethylene- polyphenylene- isocyanate Atlox- polyoxyethylene- sorbitol- hexaoleate Wettol - Phenol sulfonic acid - sodium salt HMDA - Hexamethylenediamine

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

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

Claims

Claims of the patent
1. A microencapsulated insecticide product comprising as active ingredient 0.001-80 w % IRcisS/l ScisR and/or IRtransS/l StransR 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 I RcisS/l ScisR and/or I RtransS/l StransR 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 foπnaldehyde, 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 foπned 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. -1 1. 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, preferable propylenglycol 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 adliesive preferably polyvinyl- pyrrohdone and lactose.
PCT/HU1996/000060 1995-10-20 1996-10-16 Microencapsulated insecticide preparations and a process for the preparation thereof WO1997014308A1 (en)

Priority Applications (2)

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HU9503021 1995-10-20
HUP9503021 1995-10-20

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JP51563997A JPH11514360A (en) 1995-10-20 1996-10-16 Microencapsulation insecticide preparations and a method of manufacturing the same
CA 2235280 CA2235280A1 (en) 1995-10-20 1996-10-16 Microencapsulated insecticide preparations and a process for the preparation thereof

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WO2006092409A2 (en) * 2005-03-01 2006-09-08 Basf Aktiengesellschaft Fast-release microcapsule products
WO2006111553A1 (en) * 2005-04-22 2006-10-26 Endura S.P.A. Innovative formulation
WO2006111839A1 (en) * 2005-04-22 2006-10-26 Chemia S.P.A. Preparation of compositions with high insecticidal activity
ES2332639A1 (en) * 2007-09-05 2010-02-09 Sumitomo Chemical Company, Limited Pesticide composition.
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Cited By (16)

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Publication number Priority date Publication date Assignee Title
US9079152B2 (en) 2003-05-11 2015-07-14 Ben Gurion University Of The Negev Research And Development Authority Encapsulated essential oils
WO2004098767A1 (en) * 2003-05-11 2004-11-18 Ben Gurion University Of The Negev Research And Development Authority Encapsulated essential oils
WO2006092409A3 (en) * 2005-03-01 2007-03-22 Basf Ag Fast-release microcapsule products
WO2006092409A2 (en) * 2005-03-01 2006-09-08 Basf Aktiengesellschaft Fast-release microcapsule products
EP2133140A3 (en) * 2005-03-01 2010-04-07 Basf Se Fast-release microcapsule products
WO2006111839A1 (en) * 2005-04-22 2006-10-26 Chemia S.P.A. Preparation of compositions with high insecticidal activity
US8025894B2 (en) 2005-04-22 2011-09-27 Endura S.P.A. Innovative formulation
WO2006111553A1 (en) * 2005-04-22 2006-10-26 Endura S.P.A. Innovative formulation
US9775340B2 (en) 2005-04-22 2017-10-03 Endura S.P.A. Biologically active formulation
ES2332639A1 (en) * 2007-09-05 2010-02-09 Sumitomo Chemical Company, Limited Pesticide composition.
ES2332640A1 (en) * 2007-09-05 2010-02-09 Sumitomo Chemical Company Limited Pesticide composition.
ES2332638A1 (en) * 2007-09-05 2010-02-09 Sumitomo Chemical Company, Limited Pesticide composition.
JP2013517314A (en) * 2010-01-22 2013-05-16 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se A method for controlling arthropods, including the spot-like application of the gel
EP2589290A1 (en) 2011-11-04 2013-05-08 Endura S.p.a. Microcapsules comprising a pyrethroid and/or neonicontinoid and a synergizing agent
US9044012B2 (en) 2011-11-04 2015-06-02 Endura S.P.A. Use of formulations having insecticidal activity
WO2014009269A1 (en) * 2012-07-11 2014-01-16 Endura S.P.A Insecticidal formulations of microcapsules

Also Published As

Publication number Publication date Type
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