OA16333A - Insecticide-comprising polymer material. - Google Patents

Abstract

The present invention relates to an insecticide-comprising polymer material which comprises at least one embedded insecticidal active substance in the polymer matrix and which has outstanding biological activity, and to the product prepared from this polymer and their use for protecting humans, animals and plants against arthropods, in particular for controlling insects.

Description

The présent invention relates to an insecticide-containîng polymeric material contaîning at least one embedded insecticidally active ingrédient in the polymeric matrix and having excellent biological activîty, and also to the products produced from this polymer and to their use for protecting humans, animais and plants against arthropods, particularly for controlling insects.

It is well known that humans can be protected in their sleep from arthropod stings by insecticide-coated sleeping I nets. This is particularly important in countries in which arthropods transmit diseases (malaria for example). Coated fabrics can also be used as drapes in front of Windows or doors in order to control arthropods entering dwellings. Similarly, using coated fabrips to cover vegetableé or fruits is known as a way of protecting against arthropods. This makes it possible to minimize the contamination with insecticides of the plant parts which are eaten later.

The prior art discloses thermoplastic materials contaîning insecticidally active ingrédients.

The known materials forl nets are essentially polyesters, especially polyethylene terephthalate and polyethylene, which, however, only hâve limited durability (polyester in particular) and partly hâve surfaces sensed to be unpleasantly brittle to the touch (polyethylene in particular). Therefore, it would be désirable to develop materials based on other, more durable and mechanically more robust polymers.

W0-A2 2008/004711 discloses for example netlike insecticide-containîng materials based on polyolefins such as polyethylene and/or polyprppylene. Pyrethroids are mentioned as suitable insecticidally active ingrédients. The, insecticidal material is produced by meltcompounding the thermoplastic polymer with the insecticide and then extruding the material.

WO-A 2008/032844 likewise describes an insect-repelling material obtained by meltspinning a mixture of insecticide and polyethylene. Pyrethroids are mentioned as possible insecticides. ; , .....

The use of polypropylene is also known from insecticidal evaporator platelets (for example WO 97/29634, WO 99/01030, WO 05/044001). In insecticidal evaporator platelets, an insecticidally active ingrédient is embedded into a polypropylene matrix and quickly released by heating to above 100°C h order to treat a room for example. A room-temperature use or the use in long-acting materials is not described there, nor a combination with additives.

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However, the materials known from the prîbr art hâve the disadvantage of satisfying the criteria of the WHOPES diréctive (see “Guidelines for laboratory and field testing of longlasting insecticidal mosquitp nets, 2005, http://www.who.int/whopes/guidelines/en/) for insecticide-containing long-lasting mosquito nets up to 20 washes only, which means that 5 such materials tend to lose active ingrédient at such a high rate that they will hâve lost their biologieal activity after just 20 wash cycles or so.

The loss of active ingrédient! from a textile fabric treated with active ingrédient, for example from a net treated with insecticide, can be described in terms of a rétention index (see: Report of the Eleventh i/VHOPES Working Group Meeting”, WHO, HQ, Geneva, 10 10-13 December 2007, Annéx 1). To détermine its rétention index, the polymerîc material is repeatedly subjected to a treatment defined in the WHOPES directive.

According to the WHOPES Phase I directive, the tested textiles shall still hâve a certain biologieal activity after they hâve been subjected to 20 washes. Either knock-down at 60 minutes post-exposure has to be between 95% and 100%, or the mortality at 24 hours 15 post-exposure has to be between 80% and- '400%. Knock-down after exposure of mosquitoes to insecticides is considered to bethe first visible evidence of the efficacy of an insecticide: the mosquitoes' are no longer capable of coordinated movement, fiight or walking, and usually fall on their backs without, however, being already dead.

Prior to the treatment and] following the treatment, the active-ingredient content of the mixture of polymer and active ingrédient is determined, The rétention index after n treatments is calculated frorin the n-th root of active-ingredient content after n treatments divided by active-ingredient content prior to treatment.

Textile fabrics used for vector control desirably hâve a rétention index above 95% in order that there may be sufficienj biologieal activity even after 35 wash cycles, The polymeric insecticide-containing materials known from the prior art hâve însufficient rétention indices

I (between 50 and 90% after 5 washes) which only ensure efficacy of the material for a comparatively small number of washes and hencé for â shorter use life.

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There is a further problem in that when deltamethrin is used as active ingrédient 2 weeks of storage at 54°C of the insecticide-containing . polymeric material or the nets produced therefrom will witness a conversion of the desired S-tx-isomer into the undesired R-a-isomer.

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The présent invention therefore has for its object'to provide nove! polymeric, insecticide containing materials, more based on polypropylene, which exhibit sufficient stability of the active ingrédient even after storage, preferably of 2 weeks at 54°C, to ensure sufficient efficacy on the parti of the material.· it is likewise an object of the présent invention to provide an insecticide-containing netlike polymeric fabric which meets the requirements of the abovementioned WHOPES directive. Iri addition, the amount of active-ingredient component to be used should be kept as low as possible without compromising the insecticidal effect. Further desiderata are a fast-acting insectîcidal effect, a uniform release of active ingrédient and also a very simple and inexpensive process of production.

We hâve found that these 'objects are achieved by the polymeric insecticide-containing material of the présent invention and also by the insecticide-containing netlike polymeric fabrics produced therefrom. | i

The présent invention accordingly provides an insecticide-containing polymeric material containing deltamethrin and also a UV stabilizef, characterized in that the material includes a less than 10%, preferably less then 8% and* more preferably less than 6% R-a-isomer fraction of the deltamethrin. It is very particularly'préférable for the R-a-isomer fraction to be between 0% and 5%. |

The présent invention likewiée proyides a netlike fabric based on the insecticide-containing polymeric material of the présent invention.

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Such a netlike fabric, containing the polymeric material of the présent invention, preferably has in accordance with WHOPES directive (Phase I) a knock-down after 60 minutes of between 95% and 100% oria mortality after 24 hours of between 80% and 100% after at least 25, preferably at least 30 and even more preferably at least 35 washes.

In addition, the netlike fabric^ containing the polymeric material of the présent invention are characterized in that after at least 5 washes in accordance with the WHOPES report they hâve a rétention index r of thé formula (I) ^! , γ where t_n = total active-ingredient content after n washfes (g/kg),

-4t₀ = total active-ingredient content after 0 washes (g/kg) and i

n = number of washes, of at least 95%.

The netlike fabric containing the polymeric material of the présent invention preferably has a régénération time of less than 24, preferably of less than 8 and more preferably of less than 2 hours (tested in accordance with yVHOPES directive (phase 1)).

According to the présent invention, the “WHOPES directive is to be understood as meaning the directive “Guidelines for laboratory and field testing of long-lasting insecticidal mosquito nets, 2005). This directive is retrievable at the following internet address: http://www.who.int/whopes/qLiidelines/en/·

According to the WHOPESi directive, a “washing is defined as follows: a netlike fabric (25 cm x 25 cm) is introduced into a 1 litre beaker containing 0.5 litres of deionized water and 2 g/l of “Savon de Marseille soap (pH 10-11) added just before the netlike fabric and fully dissolved in the deionized water. After addition of the netlike fabric, the beaker is immediately introduced into a warm water bath at 30°C and shaken for 10 minutes at 155 movements per minute. The netlike fabrics are then removed from the beaker and rinsed twice for 10 minutes at a timé with clean, deionized water in the same shaking conditions as mentioned above. Thereafteij, the netlike fabrics are dried at room température and stored at 30°C in the dark between thé washings. A '

According to the présent invéntion, the term “knock-down describes the state of an animal on its back or side, which isistill capable of uncoordinated movement up to short periods of flying.

According to the présent invention, the term “mortality describes an immobile state of an animal on its back or side.

According to the présent invention, the term “régénération time” describes the time which passes until the original efficacy is restored .1

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Polymeric materials to be used according to the^! présent invention are polypropylene and also polypropylene copolymers. Preference is given to using polypropylene. A multiplicity of polypropylenes are known from the prior art. Polypropylenes can in principle be distinguished according to their manner of synthesis. The main proportion of polypropylenes

-5is produced in the presence of Ziegler-Natta catalysts in the suspension process or more particularly in the so-called gias phase process (cf. Kaiser “Kunststoffchemie für Ingenieure, pages 246 to 254), The gas phase process can also utilize spécifie catalysts such as metallocenes. The polymers iproduced using metallocene catalysts are particularly useful as polymeric matrix for the insecticide-containing polymeric material of the présent invention. The melting points of polypropylenes produced using metallocene catalysts are usually distinctly below those available using conventional,heterogeneous catalyst Systems, Defects dîstributed randomly along (he polymer chain cause metallocene polypropylenes, which generally hâve melting points between 135 and 150°C, to be less capable of crystallizing. The use of metallocenes as catalysts for the synthèsis of polypropylenes also permits better stéréospecific polymerization, i.e. the tacticity of the polypropylenes and hence their properties are easier to control. Polypropylenes' catalysed using metallocenes hâve a narrower molar mass distribution, i.e. they contain virtually no heptane solubles anymore.

In addition to the type of catalyst used in their synthesis, polypropylenes can also be distinguished according to the spatial arrangement of the side groups of the carbon main chain. There is isotactic polypropylene, atactic polypropylene and syndiotactic polypropyiene, although these forms can also occur in mixtures, The insecticide-containing polyolefin material of the présent invention preferably utilizes polypropylene having a predominantly isotactic structure.

Polypropylenes can be further distinguished according to their respective areas of use. The properties of the polymers | are specifically optimized inter alla for the requirements in injection moulding, in extrusion, in blow rrtouldïng, in pressing, in calendering and in melt spinning. The insecticide-containing polymeric material of the présent invention preferably utilizes polypropylenes interlded for the melt-spinning process to produce filaments, fibres and spunbondeds. Particular préférence is glvën to using polypropylenes useful for the production of multifilament fibres having a low denier of 50 to 150 denier, These are for example polymers bearing the brand names Metocene® and Moplen® (from LyondelIBasell, Netherlands), Repol® (Reliahce Industries Limited, India), Yuplen® (SK corporation, South Korea), Seetec® (LG Chemical, South Korea) and Achieve® (ExxonMobile Chemical Company, USA). Particular preference is given to metallocene-catalysed polypropylenes, for example Metocene® HM562S, melting température 145°C (from LyondelIBasell, Netherlands) and Achieve® 3845 (ExxonMobile Chemical Company, USA).

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The polymeric materials used can be produced with the addition of additives which are incorporated into the polymer to stabilîze or improve its processing properties, Suitable additives are for example alkylated monophenols, alkylthiomethyl phénols, hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, O-, N- and S-benzyl 5 compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, acylaminophenols, esters of p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, , esters of p-(5-tert-butyl-4-hydroxy-3methylphenyl)propionic acid with mono- or polyhydric alcohols, esters of p-(3,5-dicyclohexyl-

4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, esters of 3,5-di-tert-butyl10 4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, amides of p-(3,5-di-tert-butyl4-hydroxyphenyl)propionic âcid, ascorbic acid (Vitamin C) and aminic antioxidants. It is likewise possible to use thiosynergists, secondary antioxidants, phosphites and phosphonites.

* i it is likewise possible to produce the polymeric materials used by using métal deactivators, 15 peroxide scavengers, basic costabilizers, nucleating agents, plasticizers, lubricants, ¹ I emulsifiers, pigments, viscosity modifiera, catalysts, flow control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents, benzofuranones and indolinones, fluorescent plasticizers, mould release agents, flame-retardant additives, antistatic agents such as sulphonate salts, pigments and also organic and inorganic dyes 20 and also compounds contaîniing epoxy groups or anhydride groups.

The présent invention provides a process for producing the insecticide-containing polymeric material of the présent invention, characterized. in that first the polymer to be used, preferably polypropylene, deltamethrin and also' a UV stabilizer and optionally further insecticides or additives are melted together or separately at températures between 120 and 25 250°C, preferably 150 and 230°C, and subsequently the cooling and solidifying of the polymeric mixture takes plaoe and also the subdivision of the latter into pellets.

In addition to insecticides, it is preferably possible to use UV stabilizers (i.e. UV absorbera and/or light stabilizers) in an amount of 0.01% to 15% by weight, more preferably 0.03% to

8% by weight, based on the total mass of the composition of the insecticide-containing polymeric material. UV absorbera and light stabilizers useful for carrying out the process are for example 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of substituted and unsubstîtuted benzoic acids, acrylates, nickel compounds, sterically , 2-(2-hydroxyphenyl)-1,3,5-triazines and also mixtures thereof.

hindered amines, oxamides

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-7Preferably no sterically urjhindered amines are used as UV stabilizers, but 2-(2hydroxyphenyl)benzotriazole$, 2-hydroxybenzophenones, esters of substituted and unsubstituted benzoic acids,! acrylates, nickel compounds, oxamides, 2-(2-hydroxyphenyl)1,3,5-triazines and also mixtüres thereof arè used, Particular preference is given to triazine compounds and butrimezole, Very particular preference is given to phénol, 2-(2Hbenzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (CAS 125304-04-3) and 2-(5chloro-2H-benzotriazol-2-y 1)-6-(1,1-dimethyiethyl)-4-methylphenol (CAS 3896-11-5).

The polymaterial to be used Is for example melted in a single-screw extruder, a twin-screw extruder, a multi-screw extruder or a co-kneader,

The single-screw extruder used can be for example a smooth or grooved barrel extruder or a Transfermix. A grooved barrel extruder is preferred, i,

Twin-screw extruders may be co- or counter-rotatîng. Twin-screw extruders may further be close-meshing or non-intermeshing. Preference is given to a close-meshing corotating configuration.,

Multi-screw extruders hâve at least three screws, preferably four to twelve. The screws may

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each be arranged to form .close-meshing pairs, in which case the screw pairs can be arranged tangentially and cpunter-rotating relative to each other. The screws of a multiscrew extruder can further be ail corotating, in which case each screw intermeshes in two neighbouring screws. A spécial form of multi-screw extruder is the planetary roil extruder wherein a driven central spindle drives freely revolving planetary spindles which in turn circulate in a fixed housing.! The central spindle, the planetary spindles and the housings hâve toothed-wheel intermeshing.

The process of the présent invention is particularly preferably carried out using a closemeshing corotating twin-screw extruder.

The construction of the extruder screw is adapted to the respective application scénario.

Room température solid insecticides, UV stabilizers and further additives are preferably metered together with the startîng polymer pellet^ into the feed zone of the extrader. In another preferred embodiment, room température solid insecticides, UV stabilizers and other additives are melted and metered in liquid form. The extruder housings are température controlled to 4 to 250°C. The extruder housing at the feed zone of the extrader is preferably cooled to 4 to 50°C. The remaining extruder housings are preferably température controlled

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-8to 100 to 250°C and more preferably to 140 to 250°C. In the extrader, the polymer and, depending on the melting point, the insecticide as well and also the UV stabilizer are melted and mixed. The mixture is extruded through a holedie generally known to a person skilled in the art and peiletized. The additives may also comprise further inorganic or organic fillers such as for example organic pigments, titanium dioxide, carbon black or talcum.

The résidence times in which the polymer is liquid during melting and mixing are between 3 I -··! li ’ .

and 300 seconds, preferably between 5 and 120 seconds and more preferably between 8 and 30 seconds. i

The mixing of the insecticide and of the UV stabilizer and also further additives with the molten polymer can take place in the same apparatus in which the melting of the polymer takes place, or in a further apparatus. Ail the abovementioned extruders are suitable for the mixing. A further possibility is to mix the insecticide and, where appropriate, the additives with the polymer in a static mixer. The mixing is preferably carried out with a static mixer.

When the insecticide or the additives is added in liquid form, it is generally melted and intermediately stored in an initial charge vessel, from which it is then conveyed into the mixing apparatus. The conveying can be effected for example via a pump or via an increased admission pressure. The température of the initial charge vessel is chosen such that the insecticide is stable and the viscosity of the insecticide is sufficiently small to ensure good pumpability. It is advantageous in this caseWheat the initial charge vessel, the pump and ail lines. The metering into the mixing apparatus preferably proceeds via a needle valve. The metered amount of insecticide is preferably measured by a suitable mass flow rate meter, for example according to the Coriolis principle or according to the heated wire principle, and closed-loop coritrolled to small déviations via the pump or a valve.

Room température liquid insecticides are added to the already molten polymer in a processing zone of the extrader via a needle valve. Depending on the viscosity and melting point of the insecticide, the insecticides, UV stabilizers and other additives or their mixture i are heated for this. i process wherein one or more dies extrade continuous strands i 1

After mixing, a preferred embodiment comprises booling and solidifying of the polymeric materials and also subdivision into pellets. This ca’n be accomplished for example using the common strand pelletization which are then air or water cooled to solidify them and subsequently comminuted to the desired size in a pelletizer. Suitable dies are known to a person skilled in the art. Underwater

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-9pelletization is a further method, the meit emerging from the die underwater, being eut there and by a circulating biade and subsequently water cooled, thereafter screened off and dried. A further method is water ring pelletization where the polymer is eut in the liquid-melt state in air and thereafter whizzed by centrifugal forces in a rotating water ring to cool. Particular preference is given to the method of underwater pelletization and to the strand pelletization process. .·

The présent invention likewise provides pellets containing the insecticide-containing ' I J polymeric material ofthe présent invention.

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In one embodiment of the process of the présent invention, only polymeric material produced by the mixing operation is'fed to a subséquent processing operation. The amount of insecticide in the simple mixing operation is in the range from 0.05% to 15% by weight, preferably in the range fromÎO.2% to 10% by weight and more preferably in the range from 0.4% to 8% by weight, based on the total mass.

In a further embodiment, a polymeric material having an increased concentration of insecticidally active ingrédient is produced in peÎJet form (known as a masterbatch) and fed to a subséquent processing operation in a mixture with untreated polymer. In this case, the concentration of insecticide in the masterbatch polymeric material of the présent invention is increased, preferably to a concentration between:3 to 20% by weight and more preferably 5% to 15% by weight based on the total mass.

A further embodiment comprises a first step of producing the polymeric material of the présent invention as a masterbatch which thereafter, by melting and mixing with untreated polymer and possible further additives, is again further processed into a polymeric material of the présent invention, which is generated in the form of pellets.

The subséquent processing [opération may comprise for example the resulting pellets of the polymeric material ofthe présent invention being processed in a processing step into shaped articles such as for example foils, air-cushioning materials, films, profiles, sheets, wires, threads, tapes, cable and pipe linings, casings for electrical instruments (for example in switchboxes, aircraft, refrigerators, etc.). Preference is given to producing foils in an extrusion operation. These skilled in the art knows methods whereby multilaÿered foils can be produced. These include for example coextrusion or lamination. Preferenceis given to a multilaÿered foil consisting of one layer of material according to the présent invention and also of one or more layers of foils can be produced to hâve one or more layers. A person

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-ÎOanother material. These othër materials can be for example polyethylene (HDPE, LDPE, LLDPE) or polyethylene copolymers, polypropylene, adhesion investigators such as for example ethylene-vinyl acetate copolymer, polyamide, polycarbonate, polyvinyl chloride, polystyrène, polyesters such as for example polyethylene terephthalate or polybutylene terephthalate, cellophane, polylactide, cellulose acetate or blends thereof. These polymers can be présent in pure form or as blends and may contain additives and further inorganic or organic fillers such as for example organic pigments, titanium dioxide, carbon black or talcum.

It is particularly préférable for the 'subséquent processing operation to consist in further processing the insecticide-containing polymeric material in a subséquent spinning operation to form fibres, yarns, filaments or threads.

The polymeric material of the présent invention preferably utilizes deltamethrin as insecticîdally active ingrédient. However, it is also possible for further însecticidally active ingrédients to be admixed. Suitable additional insecticides are insecticides from the classes

I of the org a no phosphates, pyrethroids, neonicotinoids and carbamates.

Organophosphates include for example acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos(-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos, dimethoate, t

dimethylvinphos, dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, ) fensulfothion, ferithion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl O-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion •i‘ ; . >

(-methyl/-ethyl), phenthoatë, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridàphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, (erbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion.

The pyrethroids include for example acrinathrin, allethrin (d-cis-trans, d-trans), beta cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cîs-Cypermethrin, cis-Resmethrin, cis-

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- Il Permethrin, clocythrin, cyclpprothrin, cyfluthrin, ,cyhalothrin, cypermethrin (alpha-, beta-, thêta-, zêta-), cyphenothrin, déltamethrin, ^empenthrin (1R-isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (1R-trans isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, tauFluvalinate, tefluthrin, terallethrin, tetramethrin (-1R- isomer), tralomethrin, transfluthrin, ZXI 8901 and pyrethrin (pyrethrum). Preference according to the présent invention is given to beta-cyfluthrin, bifenthrin, cyfluthrin, deltamethrin and transfluthrin, Particular preference according to the présent invention is given to beta-cyfluthrin, cyfluthrin, deltamethrin, permethrin (cis-, trans-) and transfluthrin.

The neonicotinoids include for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thîacloprid and thiamethoxam. Preference according to the présent invention is given to imidacloprid and clothianidin, ‘^{? J} ; i?

The carbamates include for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacàrb, butocarboxim, butoxycarboxim, carbaryl, i

carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate. Preference according to the présent invention is given to bendiocarb and carbaryl, ¹

Further insecticidally active ingrédients are for example DDT, indoxacarb, nicotine, bensultap, cartap, spinosad, camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole, avermectin, emamectin, emamectin-benzoate, ivermectin, milbemycin, diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene, chromafenozide, halofenozide, methoxyfenozide, tebufenozide, bistrifluron, chlofluazuron, diflubenzurbn, fluazuron, _: fluçyçloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noyiflumuron, penfluron, teflubenzuron, triflumuron, buprofezin, cyromazine, diafenthiuron, azocyclotin, cyhexatin, fenbutatin-oxide, chlorfenapyr, binapacyrl, dinobuton, dinocap, DNOC, fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, hydramethylnon, dicofol, rotenone, acequinocyl, fluacrypyrim, Bacillus thuringiensis s rains, spirodiclofen, spiromesifen, spîrotetramat, 3-(2,5-

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- 12dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-y) ethyl carbonate (alias: carbonîc acid, 3-(2_]5-dimethylphenyl)-8-methbxy-2-oxo-1-azaspiro[4,5]dec-3-en~4-yl ethyl ester, CAS-Reg.-No.: 382608-10-8), flonicamid, amitraz, propargite, flubendiamide, rynoxapyr, chloranthranilîprol, thîocyclam hydrogen oxalate, thiosultap-sodium, azadirachtin, Bacillus spec., Beauveria spec.,-Codlemone,'Metatthizium spec., Paecilomyces spec,, Thuringiensin, Verticillium spec.,_; aluminium ^phbsphid, methylbromide, sulfurylfluorid, cryolite, flonicamid, pymetrozine, clofentezine, etoxazole, hexythiazox, amidoflumet, benclothiaz, benzoximate, ' bifenazate, bromopropylate, buprofezin, chinomethionat, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone, japonilure, metoxadiazone, petroleum, piperonylbutoxid, kaliumoleat, pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene and verbutin.

The insecticides mentioned can be used individually or in mixtures.

Preferred insecticides are beta-cyfluthrin, pèrmëthrin (cis-, trans-), transfluthrin, bendiocarb, clothianidin, imidacloprid, thiacloprid, ethiprol, fipronil, rynoxapyr, chlorpyriphos-methyl, chlorfenapyr. Particular préférence is given td beta-cyfluthrin, transfluthrin, bendiocarb, clothianidin, ethiprol and rynoxapyr. > ^:

The concentration of the insecticidally active .ingrédients in the polymeric material can be varied within a relatively wide concentration range, for example 0.05% to 15% by weight, preferably 0.2% to 10% by vÿeight, more preferably.0.4% to 8% by weight. The concentration shall be chosen according tb the field of application such that the requirements concerning insecticidal efficacy, durability and toxicîty are met. Adapting the properties of the material can also be accomplished by mixing insecticides in the polymeric material by the blending of materials according to the ptesent invention which contain different insecticides, or by using materials according to the présent invention which contain different insecticides which are used in combination with eiach other, for example as mosaic nets. Custom-tailored textile i

fabrics are obtainable in this way.

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The présent invention provides a process for producing filaments, fibres, threads and yarns, characterized in that the insecticide-containîng polymeric material of the présent invention is initially melted, formed into spun threads and cooled, the spun threads obtained are led through a drawing system and drawn and then optionally the setting of the filaments, fibres, threads and yarns takes place.

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- 13 In this process, a spin finish is preferably used during the spinning operation.

The threads or filaments are produced, after the mixing operation, by melt spinning as described for example in DE-A 41 36 694 (page 2, Unes 27-38, page 5, line 45 - page 6, line 23) or DE-A 10 2005 054; 653 ([0002]). In this process, the insecticidal polymer produced is melted in a single-screw extruder and forced with the aid of a gear pump through a die plate. The die plate is preceded by a filter pack. The polymer strands emerging from the die plate are subjected to high-speed drawing, spin finishing and winding up.

The melt-spinning process comprises the steps of:

1.

preparing the spinning melt

2.

melt spinning

3.

cooling

4.

spin finishing

5.

drawing

6.

aftertreating

The fibres are produced from the molten polymeric material of the présent invention using the known melt-spinning processes. Préférence: is given to processes for producing monofilament fibres, multifilàment fibres, fibrous nonwoven webs, hollow fibres, staple fibres, multicomponent fibres and matrix-embedded microfibers. The production of multifilàment fibres is particularly preferred.

In step (1), the polymeric material of the présent invention, produced by the mixing operation, is melted at températures of at least 10°C below the décomposition température and at least 5°C above the melting point of the polymeric material and conveyed without cooling to the spinnerette die pack. The polymeric material is preferably melted and spun at a température below 250°C| more preferably below 235°C.

Fibre production can be carried out in one stage by the polymeric material being fed to the spinning operation directly after mixing, in molten form. It is similarly possible to carry out a two-stage process wherein the previously produced pellets composed of the above25

i

-14described polymeric materiaj are melted in a conveyor extruder or in a heatable flask and conveyed to the spin pack.

In a preferred embodiment^ the insecticide-containing polymeric material of the présent invention is fed to the spinnirig operation directly after mixing, in molten form.

It is particularly préférable for the insecticide-containing masterbatch polymeric material of the présent invention, having an increased insecticide concentration, to be mixed with purely ' .i f polymer material in the course of the spinning opération. It is préférable for the polymeric material used to be only pplypropylene which .has been prepared with metallocenes as catalyst. This mixing can bel effected in different ways. In one embodiment, the insecticidecontaining polymeric material and the additional polymeric material are fed via two separate ' ·’,-ί ‘ metering assemblies to the,single-screw extruder in which the materials are melted. In a further embodiment, the two polymeric materials are mixed prior to addition into the singlescrew extruder and then supplied to the extruder in the form of a premix. In a further embodiment, the insecticide-containing polymer and the unloaded polymeric material are melted in two separate extruders and these two streams of melt are subsequently mixed with each other. ^!

The spinnerette die pack consists of a known construction. The spinnerette die plate can hâve one to several thousand die holes having hole diameters customary for fibre production. After the spinnerette die pack, the spun threads pass through a cooling sector,

I * · A !

are spin finished and wound up or deposited in cans. The cooling medium used is a liquid or a gas. When it is a liquid, water is used. Dry cooling sectors take the form of quenching chambers in which the spun threads are cooled down with cold air, nitrogen or carbon dioxide being used as cooling gas.

A spin finish is applied to the fibres in the coùrseof the spinning operation. Application ofthe 25 spin finish modifies the surface properties of the fibres. The spin finish inter alia reduces the friction between métal and thread and between thread and thread, and also reduces the antistatic charging of the fibres. The application of a spin finish is necessary to carry out the melt-spinning operation. Without an appropriate spin finish, the winding and unwinding and further processing of filament yarns is not possible. A person skilled in the art knows how to adapt a spin finish for this purpose. Spin finîshes are also known to a person skilled in the art. The amount of the apalred nonaqueous constituents of the spin finish is in the range from 0.1% to 2.0% by weight and preferably in the range from 0.5% to 1.5% based on the total mass of the fibre.

-.15The spin finish can be applied at the point of.exit from or entry to the fibre production line, the winding/take-off machine; the rewinding machine and/or the quench chamber.

The spin finish, or to be morë précisé the mixture of spin finish and water, can be applied to the fibre in various ways. In principle, it can be applied by spraying, swapping, rolls, rods and pins.

The spin finish can be meteringly added in one or two or in a plurality of stages.

The wound-up or depositedi spun threads can then be led through a drawing system and drawn and wound up as fiat filament, or optionally be crimped, set or eut into staple fibres.

Preferably, the spinnîng and drawing operations are carried out in one system without intermediate winding up of the undrawn filaments. Suitable drawing Systems are draw-twist or draw-wind machines for fiat multifilaments, compact monofil spin-draw Systems for monofilaments, draw production lines and compact spin-draw Systems for staple fibres. The drawing Systems can be equipped with heatable or partly non-heatable godets or draw rolls, and also guide rollers, further with steam, hot-àir and infrared ducts, coating devices, crimping units, dryers, cutting Systems and other units. The drawing operation can be followed by any known finishing measure, such as the application of a spin finish or a coating for example.

Setting the filaments or fibres is usually carried out on these Systems after the drawing step.

The multifilaments spun atlhigh speed can be draw-textured on machines known for this i

purpose, and similarly the drawn multifilaments can₍be textured.

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Multifilaments preferred according to the présent invention hâve 1 to 100 filaments, more preferably 5 to 75 filaments and most preferably 10 to 60 filaments.

The présent invention further provides threads, yarns, fibres or filaments containing the ; J insecticide-containing polymeric materials of the présent invention.

i

According to the présent invention, fibres having a linear density of 1000 to 10 denier, preferably 500 to 20 denier and more preferably 200 to 50 denier are used.

I ubsequently be further processed into any desired products such

The threads, yarns, fibres pr filaments thus produced, containing the polymeric material of the présent invention, can s as for example textile fabrics. Preference is given for example to wovens, braids, knits, felts

or nonwovens. Particular préférence is given to netlike fabrics such as sleeping nets for example,

The production of wovens and braids is effected by means of two thread Systems (warp and weft) crossing each other at tight angles. A knitted fabric can be produced from one thread 5 (one-thread knit) or be constructed from two or more threads (warp-thread knit) according to the warp-thread technique.’ These fabrics are produced on loop-forming or -drawing machines. It is further possible to use short threads or thread pièces to produce felts or nonwovens. ,

To produce netlike fabrics bÿ means of loop-forming and -drawing processes, it is necessary lû to produce a so-calîed warp beam. The polymeric threads are wound in equal length in a parallel arrangement on a bobbin, the so-called warp beam.

To render the polymeric threads more lubricious and robust during processing into a textile fabric, the threads are frequéntly sized, i.e. coated with a protective film of starch or synthetic sizes. Sizing can be effected using a winding oil which is applied during warp-beam 15 production in order to improve the winding properties during warp-beam production and to reduce thread-on-thread friction and also friction between métal and thread. Reducing friction is important not only for warp-beam production but also for the subséquent loopforming operation. i

Prior to further treatment (for example bleaching and dyeing), textile fabrics composed of 20 manufactured fibres are generally washed, since the manufactured fibres contain small amounts of additives at the fibre surface. These additives comprise more particularly the above-described spin finishfes, but other additives such as possibly applied sizes are also removed in the process. This washing operation may be carried out in various ways generally known to a person skilled in the art. In some processes, the washing liquor is 25 agitated, in other fibres the textile fabric moves through the quiescent washing liquor.

ΐ^p

Possible processes are pulsed washers, jet washers, washing on sieve drums, pad-mangles j ' ^v and also vacuum processes. Continuous processes are preferred on an industrial scale.

and polyethylene fibres, this operation is not carried out in the sxtile fabrics composed of these polymers cannot be dyed with a

In the case of polypropylen prior art processes since te dyebath. This holds more particularly for the production of mosquito nets, since in this case the textile fabric is not subjected to any further finishing operation apart from heat setting.

- I7Surprisingly, however, the washing of the netlike fa bric of the présent invention with water and a detergent prior to the heat-setting step has been found to hâve a positive effect on the loss of insecticide during washing 'according to the WHOPES guideline. Ail the washing processes described above (i.e. pulsed washers, jet washers, washing on sieve drums, padmangles and also vacuum processes) can be used for this washing operation.

The fabric thus produced has very ielastic properties'freqdently and is not form stable. In this form, it is more particularly unsuitabîe for the p'rôcluction of mosquito nets, since this use has spécifie requirements in terms of shrinkage determined to DlN EN ISO 5077. Therefore, it is preferred to carry out a heat-setting operation. Heat setting can be carried out with hot water, saturated steam or hot air, or in a dry atmosphère. Preference is given to carrying out heat setting in a normal atmosphère without addition of water or steam. Heat setting is preferably carried out using a continuous process in which the textile fabric is fixed on a stenter and led through an oven on a stenter. This oven is preferably subdivided into two or more heating zones which can be individually température controlled. During the thermal treatment, the textile fabric can be concurrently subjected to mechanical loading to a varying degree by : . L ^r _r · stretching. This is done by moving the two sides of.the stenter apart in the setting oven until the desired width is reachedifor the formed-loop knit.

The température to heat-sét the netlike fabric containing the polymeric material of the présent invention is choseri 20°.C, preferably 1Q°C., below the melting température of the polymer. Surprisingly, heat setting at a few degrees below the melting température of the polymer was found to lead to a réduction in the loss of insecticide during a wash in soapy water.

In addition to the abovementioned netlike fabrics, threads, yarns, fibres or filaments can also be subjected to the washing operation of the présent invention and the heat setting of the présent invention. These materials also subsequently exhibit the technical effects described in the présent invention.

In addition to the surprisingly found effect of the setting température on the release of the insecticide from the matériel of the présent invention during washing in accordance with WHOPES directive in soapy water, the setting température and the duration of the setting operation which is determiqed via the speed at which the formed-loop knit is led through the setting oven lead to alteration of the crystal structure in the polymer. The crystal structure can be determined using DSC measurements ^DSC = Differential Scanning calorimetry (dynamic differential calorimetry)). Differential '’scanning calorimetry is a measurement

I b i | -18method known to a person s^illed in the art for determining the crystallinity of polymers. This method détermines the amopnt of heat which needs to be applied for a physical or chemical conversion of a substance. A description of the method can be found inter alia in Praxis der Thermischen Analyse von Kunststoffen”, Ehrenstein, Riedel, Trawiel, Cari Hanser Verlag, i

Munich 2003. Upon measurement at a heating rateof 10 K/min, the materials of the présent invention hâve only a low proportion of crystal structures that melt above the preferred setting température during tlje DSC measurement qnder customary conditions.

i

For example, to produce the netlike fabric of the présent invention consisting of the polypropylene HM 562 S frbm Baséli, the'duration has to be chosen such that, during a customary DSC measuremept at a heating rate of 10 K/min, the amount of crystal structures in the material of the présent invention that melts above 140°C is more than 62 J/g and preferably more than 65 J/gJ

I

The présent invention in^ecticide-containing polymeric materials or their descendent products can be successfùlly used for killing harmful or nuisance arthropode, more particularly arachnids and insects. The netlike fabrics containing the insecticide-containing material of the présent invention are preferably used for producing sleeping nets for i protection against mosquitoés.

Arachnids include mites i(e.g. Sarcoptes scabiei, Dermatophagoides pteronys-sinus, : * ^k ?*:'

Dermatophagoides farinaej Dermanyssus gallinae, Acarus siro) and ticks (e.g. Ixodes | f ricinus, Ixodes scapularis, |Argas reflexus, Ornithodorus moubata, Boophilius microplus, Amblyomma hebraeum, Rhipicephalus sanguineus);

; -r I

Sucking insects include essentially the mosquitoés, (e.g, Aedes aegypti, Aedes albopictus, Aedes vexans, Culex quinquefasciatus, Culex tarsalis, Anopheles gambiae, Anopheles albimanus, Anopheles steppensi, Mansonia titillans), sand flies (e.g. Phlebotomus papatasii), gnats (e.g. Culicoides furen

s), black flies (e.g. Simulium damnosum), biting houseflies (e.g.

Sto-moxys calcitrans), Tsetsé flies (e.g. Glossina morsitans morsitans), horseflies (e.g. Taba-nus nigrovittatus, Haématopota pluvialis, Chrysops caecutiens), common houseflies (e.g . Musca domestica, Ml sca autumnalis, Musca vetustissima, Fannia canicularis), flesh flies (e.g. Sarcophaga carnaria), myiasis-causing flies (e.g. Lucilia cuprina, Chrysomyia chloro-pyga, Hypoderma b avis, Hypoderma linéatum, Dermatobia hominis, Oestrus ovjs,

Gaste-rophilus intestînalis, Cochliomyia hominivorax), bugs (e.g. Cimex lectularius, Rhodnius prolixus, Triatoma infestans), lice (e.g. Pediculus humanis, Haematopinus suis,

I i

I ‘ -19Damalina ovis), fleas (e.g.i Pulex irritans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephali-des felis) and ^and fleas (Tunga penetrans).

Biting insects include essentially cockroaches (e.g. Blattella germanica, Periplaneta i

americana, Blatta orientalis, jSupella longipalpa), beetles (e.g. Sitiophilus granarius, Tenebrio molitor, Dermestes lardariùs, Stegobium paniceum, Anobium punctatum, Hylotrupes bajulus), termites (e.g. Reticulitermes lucifugus), ants (e.g. Lasius niger, Monomorium pharaonis), wasps (e.g. Vespula germanica) and. 'larvae of moths (e.g. Ephestia elutella, Ephestia cautella, Plodia intérpunctella, Hofmaônophila pseudospretella, Tineola bisselliella, Tinea pellionella, Trichophacja tapetzella).

The materials of the présent'invention are preferably used against insects, particularly of the order Diptera and more preferably against the suborder Nematocera.

The présent invention likewise provides for the use of the insecticide-containing material of the présent invention in the manufacture of textile fabrics such as wovens, braids, knîts, felts, nonwovens and/or in the nrianufacture of netlike fabrics such as sleeping nets, mosquito nets..

The présent invention further provides threads, yarns, fibres, filaments; netlike fabrics such as sleeping nets, mosquito nets; textile fabrics such as wovens, braids, knits, felts, nonwovens; extruded parts: such as foils, air-cushioning materials, films, profiles, sheets, i wires, threads, tapes, cable and pipe linings and casings for electrical instruments.

i . i

The présent invention fulrther provides an insecticide-containing polymeric material obtainable by the processes described above.

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A further embodiment of tlfie présent invention protects filaments, fibres, threads and/or yarns obtainable by the processes described above'.'

Examples:

Test methods: bioloav

Test insects

Female malaria mosquitoes (Anopheles gambiae, sensitive Kisumu strain), fed with sugared water only.

-20Three-minute exposure (cône test) i *

The tests were carried out using WHO standard cônes with an exposure time of 3 minutes on part-samples, The net piedes were 30 x 30 cm in size. In each case, five mosquitoes at a time were placed under onei cône and four cônes were used on a part-sample. The same sample was subsequently teisted once more with four cônes and once with two cônes, i.e. 2.5 réplications involving altoigether 50 mosquitoes.

i

After exposure, the insects were transferred into plastic cups 10 at a time and the knockdown effect was determined after 60 minutes. Knock-down is the first visible indication of the onset of action, and is characterized in that the insects lose coordination of their movements and are no longer able to fty or walk. Thereafter, sugared water was likewise administered and mortality determined after 24 hours. After the tests, the average values were computed.

Washing operation in accordance with WHOPES directive

500 ml of deionized water çontaining 0.2% (w/v) of laundry detergent (Le Chat, Henkel, France) were introduced at i30°Ç into a .1 litre glass bottle. One piece of net 30 x 30 cm in size or three pièces of net 1p x 12 cm in size were introduced into the bottle which stood on a horizontal shaker (155 movements per minute) in a water bath at 30°C. Thereafter, the water was poured out of thé bottle and the sample was rinsed twice with 500 ml of water each time for 10 minutes ag^in under shaking.

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The net samples were liné dried for two hours and thereafter additionally for at least 24 hours lying on aluminiutn foil at 27°C and 70-80% relative humidity before renewed washing or an évaluation of biological activity.

Analysis of deltamethin in polypropylenes

Part A - sample préparation:

About 1 g of material of a représentative sample (yarn, fabric or pellet) is placed in a 250 ml flask; then approximately 30 ml of xylene (PA quality) are added. The sample material is then dissolved at precisely 3 minutes in an oil bâth af190°C under reflux (water-cooled column, 20 cm) and stirring (125 révolutions pér minute, magnetic stirrer and stirring bar).

The oil bath is removed and about 10 ml of isopropanol (PA quality) are added and the flask is left to cool for about 5 minutes at room température to precipitate the polymer. Thereafter the extract is made up with 30 ml of acetonitrile.

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-21 The sample îs subsequentl), filtered off with suction (analytical filter, 5 cm diameter) and thereafter the filtrate is passéd through a fluted filter (MN 715, 240 mm). Both filtrations are

I done by washing with 10-20 iml of solvent (acetonitrile) in each case.

Finally, the filtrate is quantitiatively transferred into, a 100 ml graduated flask and made up with acetonitrile to the calibrâtion mark. γ

Part B - quantitative détermination by HPLC versus external standard:

i

The quantification of deltamethrin in samples of polypropylene extracts is carried out by means of HPLC on an Agil^nt 1100 instrument equipped with a binary pumping System. Deltamethrin and the R-alpha isomer are the target molécules of the analysis. Certified analytical standards are used as reference materials. Séparation is carried out under normal phase conditions on a Merck Lichrosorb SI 60 column (5 μ particles, dimensions 250 χ 4 mm) at 40’C column température.

The injection volume is 10 μ-Ι (sample préparation see Part A above). Séparation is effected by means of a solvent mixtùre of N-heptane and methyl tertiary-butyl ether (950+50, HPLC quality) at a flow rate of il ml per minute. The elution time under these conditions is 10 minutes. !

UV détection at a wavelength of 230 nm utilizës a diode array detector. The typical rétention time under the conditions described is about 6.3 minutes for the R-a-isomer and 7.0 minutes for the deltamethrin. | i ’

I

Production of samples: ¹

The polymeric materials of|the présent invention were produced using a corotating closei meshing twîn-screw extruder having a screw diameter of 34 mm and a housing length of

1200 mm. Extruder housing température was 200’C in ail steps and extruder speed was i

160 rpm. The feed zone oflthe extrader was cooled with water. The extruder was used to

I produce a so-called masteijbatch having a high concentration of deltamethrin. To this end,

I

10% by weight of technica grade deltamethrin (BCS AG, Monheim DE), 2% by weight of

Tinuvin® 326 FL (BASF (Ciba), ₍Ludwigslïafen, Germany) and 88% by weight of polypropylene (Metocen® HM562S, LyondelIBasell, Rotterdam, Netherlands) were mixed in the extruder (TK10). Ail the materials were. supplied in solid form to the feed zone of the extruder. The mixture emerged from the extruder in the form of strands and the strands were

-22cooled în a water bath, Subsequently, the strands were comminuted by pelletization. The pellets contained about 9.2% by weight of deltamethrin.

A second step involved ptoducing threads by diluting about 1.1% by weight of the deltamethrin-containing pelléts produced as described above with 98,9% by weight of purely polypropylene (Metocen® HÙ562S or Yuplen® H 893S (SK Corporation, Séoul, Korea). To this end, the pellets were in éach case metered into the feed zone of a single-screw extruder

I and melted and the two me|t streams subsequently combined and mixed. In the course of spinning, about 1% by weght of Stantex® 6051 spin , finish (Pulcra Chemicals GmbH, Düsseldorf, Germany) was applied to the fibres! The fibres were subsequently drawn and wound up on bobbins. Fibre thickness was 210 dtex and the fibres consisted of 25 filaments, in the second step, the fibres were drawn down to a thickness of 110 dtex. Three pairs of godets were used for drawiqg the fibres. The température of the pairs of godets was 60, 80 and 120°C. The average tenacity ofthe fibres was 4.3 cN/dtex and the residual extension of the fibres was 51%.

The two polypropylenes u$ed for dilution differ inter alia in their method of production, Metocen® HM 562S polypropylene was produced using a metallocene catalyst, while Yuplen® H 893S polypropylene was produced using a Ziegler-Natta catalyst.

The polypropylene fibres spùn were subsequently üsed to produce formed-loop knits. To this end, the first step was to prcjduce a warp beam by winding the polypropylene fibres from the individual packages in a pajrallel arrangement onto one bobbin, the so-called warp beam. These warp beams were subsequently used in a warp-knitting machine to produce the formed-loop knit.

Ormed-loop knit was subsequently subjected to a heat-setting

A portion of the untreated operation on a laboratory s^ale. This was done using a Mathis DHe 61599 type laboratory steamer. Prior to heat setting, a portion of the pièces of formed-loop knit was washed once. For 1 to 2 net pièces about 35 cm x 35 cm in size, 300 ml of 30°C tap water are admixed (Sigma-Aldrich Chemie GmbH, Munich, Germany) and is used to stir the net pièces therein for 5 min, which are subsequently wrung out and rinsed for 2 x 1 min with 300 ml of demin water at about 15The net pièces are then hung up for at least 1 h to dry. Other ere subjected to the setting operation in an unwashed state. The with 0.1% of Tween® homogenized. A glass rod

20°C (likewise with stirring) pièces of formed-loop knit w setting operation was carried out at different températures.

• i

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É ί i i' '-23The atmosphère in which thé heat setting was carried out was also varied. The heat setting was carried out in a dry atmosphère or in a water vapour saturated atmosphère.

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The samples were evaluatéd in respect of their biological activity and their loss of deltamethrin. This was followed by the repeated performance of the washing procedure of 5 the WHOPES protocol and further évaluations of the biological activity and of the loss of deltamethrin.

Results st example: Influence of spin-finish wash-off on biological activity

In this example, the fibres were produced using exclusively Metocen® HM 562S polypropylene. That îs, the dilution of the masterbatch during spinning was done with this polymer. The melting point pf Metocen® HM 562S polymer is 145^eC, according to its data sheet. Subsequently, the threads were used to produce a formed-loop knit in accordance with the operation described iabove.

The pièces of formed-loop knit were heat set for 90 seconds in a steam-containing atmosphère at different températures. One half of the pièces of formed-loop knit were i

washed in accordance with |the above-described procedure prior to heat setting in order to remove the spin finish from Jthe fibres, while the other half of the pièces of formed-loop knit were not further treated prioj· to heat setting. The spin finish was still présent on the threads of these pièces of formed-loop knit.

The pièces of formed-loop jmit were initially tested in respect of their biological activity in accordance with the above-|described procedure. Subsequently, the pièces of formed-loop knit were washed in accordance with the above-described washing operation to WHOPES directive for 5, 10, 15, 20, 25 arid 30 times in succession and each thereafter evaluated in respect of their biological activity.

)

Table 1:

Influence of spin finish on biological activity

Temperat ure of heat setting [°C]	Number of washes to WHOPES protocol H	: Knock-down after 60 min	Mortality after 24 h
Samples washed prior ί to heat ; setting	Samples unwashed prior to heat setting	Samples washed prior to heat setting	Samples unwashed prior to heat setting
110	0	; 100%	100%	100%	100%
120	0	100%	100%	100%	100%
130	0	; 100%	100%	100%	100%
140	0	100%	100%	100%	100%
110	5	100%	100%	100%	100%
120	5	; 100%	100%	100%	100%
130	5	: 100%	100%	100%	100%
140	5	: 100%	i 100%	100%	100%
110	10	1 100%	95%	95%	95%
120	10	97%	88%	97%	88%
130	10	: 98%	100%	100%	100%
140	10	100%	98%	100%	98%
110	15	; 98%	85%	94%	52%
120	15	96%	82%	96%	53%
130	15	i 100%	89% 1	95%	89%
140	15	; 100%	91%	100%	100%
110	20	100%	95%	97%	84%
120	20	98%	95%	100%	76%
130	20	; 100%	63%	100%	37%
140	20	' 100%	90%;	100%	95%
110	25	: 100%	88% ' il· :	100%	80%
120	25	95%	80%	95%	59%
130	25	98%	80%	93%	78%
140	25	. 100%	88%	98%	93%
110	30	95%	85%	100%	89%
120	30	96%	70%	96%	54%
130	30	100%	83%	100%	90%

140

30

; 100%

93%

95%

98%

The results show that washirig the spin finish off prior to heat setting achieves a significantly better biologieal effect after 1Î5 washes to WHOPES;directive.

The samples washed prior to heat setting display a clear relationship between the 5 température chosen for thie heat setting and the biologieal activity. The doser the température to the melting point of the polymer, the higher the biologieal effect.

The température at heat setting must accordingly be at most 20°C and preferably at most 10°C below the melting température of the polymer in order that a maximum biologieal i activity is achieved.

2nd example: Effect |of spin-finish wash-off on deltamethrin loss

Example 2 used the same fôrmed-loop knits whose production was described in Example 1.

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The samples were investigçited in respect of their deltamethrin content according to the procedure described above. '

-26Table 2: Loss of deltamethrin

Température of heat setting [°C]	Number of washes to WHOPES protocol [-]	Deltamethrin content	Rétention index
Samples washed prior to heat setting	Samples unwashed prior to heat setting	Samples washed prior to heat setting	Samples unwashed prior to heat setting
110	0 :	100%	100%
120	0	100%	: 100%
130	0	100%	100%
140	0	100%	100%
110	5 ;	64%	32%	91.4%	79.4%
120	5 :	69%	38%	92.8%	82.3%
130	5 :	79%	51%	95.3%	87.4%
140	5 :	82%	34%	96.0%	80.4%
110	10	53%	26%	93.8%	87.2%
120	10 :	57%	30%	94.5%	88.7%
130	10 :	63%	. 39%	95.5%	91.1%
140	10 :	84%	> 54%	98.2%	94.0%
110	15 :	52%	22%	95.8%	90.4%
120	15 :	59%	30%	96.5%	92.3%
130	15	61%·	.· 34%	96.8%	93.0%
140	15 :	79%	50%	98.5%	95.4%
110	30	43%	23%	97.2%	95.2%
120	30	49%	23%	97.6%	95.2%
130	30	53%	28%	97.9%	95.8%
140	30'	63%	39%	98.5%	96.9%

The deltamethrin content afljer heat setting was set equal to 100% and the pièces of formedloop knit were subsequently analysed for their deltamethrin content after 5, 10, 15 and 30 5 washes in accordance with the WHOPES protocol.

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The results show that température at beat setting must be at most 20°C and preferably at most 1O°C below the melting température ofthe polymerto minimize the loss of deltamethrin from the formed-loop knit of the présent invention.

3rd example: Influence of spin-finish wash-ôff on active-ingredient stability during storage i

Example 3 used the same formed-loop knits whose production was described in Example 1. The samples were investigàted, directly after production, with regard to active-ingredient stability following 2 weeks’ storage at 54°C. These storage conditions were used to sîmulate a minimum shelf-life of 2 yeàrs. Storage took place in a Heraeus Thermo Scientifics B620 drying oven. The temperatùre of 54°C was cohstantly monitored. The net samples were packed for storage in 2 to 4 layers in aluminium foil.

The samples were stored at 64’C for 2 weeks and then analysed for their deltamethrin R-aisomer content in accordancè with the method described above:

Table 3:

Fraction of R-ct-isomer after storage

Température at heat setting [°C]	; R-ü-isomer of deltamethrin
Samples unwashed prior to heat setting	Samples washed prior to heat setting
110	: 50.74%	: 5.07%
120	ί 43.58%	= 5.68%
130	45.74%	4.66%
140	51.11%	• ; 5.42%

The results show that washing off the spin finish can be used to reduce the formation of R-cc-isomer during storage tô below 10%.

4th example: Influence of atmosphère

Example 4 used the same formed-loop knits whose production was described in Example 1. The table which follows shows the influence ofthe atmosphère at heat setting on the loss of deltamethrin during the performance of washes according to the WHOPES directive. The pièces of formed-loop knit were ail heat set at140°C for 90 seconds. In the process, the atmosphère was varied in th e setting oven. Half the pièces of formed-loop knit were heat set

i in a standard atmosphère without added water or steam (dry atmosphère), while the other pièces of formed-loop knit were beat set in a standard atmosphère in the presence of steam.

Table 4: Influence of atmosphère at heat setting

Atmosphère H	Number of washes to WHOPES protocol H	Deltamethrin content [%]
Steam	0	100%
Dry	0	100%
Steam	5	82%
Dry	5	90%
Steam	io	84%
Dry	10	‘ 86%
Steam	is	79%
Dry	15	81%
Steam	30	. 63%
Dry	30	69%

The results show that when a dry atmosphère is used during heat setting the loss of deltamethrin during the wastjes to WHOPES directive is less.

5th example: Influence of polypropylene type on biological activity

In this example, the fibres were produced using Metocen® HM 562S polypropylene and Yuplen® H 893S polypropyliene, i.e. during spinning the masterbatch was in each case diluted with one of these polymers. Subsequently, the threads were used to produce a formed-loop knit in accordance with the operation described above.

The pièces of formed-loop knit were heat set in a dry atmosphère for 90 seconds at different températures. Prior to heat setting, the pièces of formed-loop knit were washed in accordance with the procedure described above’in order to remove the spin finish présent on the fibres.

After heat setting, the samples of formed-loop knit were subjected to 20 washes in accordance with the WHOF ES directive and tested in respect of their biological activity as described above.

-29Table 5: Influence of polypropylene type on biological activity after 20 washes

I

Température of heat setting [°C]	Knock-down Yuplen® H 893S	Knock-down Metocen® HM562S	Mortality Yuplen® H . 893S	Mortality Metocen® HM562S
70	90% i I	98%	74%	98%
90	64% '	98%	66%	100%
110	85%	98%	90%	100%
120	86% i	95%	74%	93%
130	100% ;	100%	100%	100%
140	100% i	100%	100%	100%

The results show that a highier biological activity is achieved when a polypropylene produced using a metallocene catalyst is used than when a polypropylene produced using a ZieglerI

Natta catalyst is used.

6th example: Influence of different UV stabilizers on isomerization of deltamethrin

The polymeric materials ofthe présent invention were produced using a corotating closemeshing twin-screw extrudér having a screw diameter of 34 mm and a housing length of 1200 mm. Extrudér housing température was 200°C in all steps and extruder speed was 10 160 rpm. The feed zone of the extruder was cooled with water. Total throughput was kg/h. ’

In a first step, polymer pellets having a concentration of 2% by weight of deltamethrin were produced. To this end, 2°Æ by weight of technical grade deltamethrin (BSC AG, Monheim DE) and 98% by weight of polypropylene (Metocen® HM562S, LyondelIBasell, Rotterdam, 15 Netherlands) were mixed iri the extruder. All the materials were supplied in solid form to the feed zone of the extruder. The mixture emerged from the extruder in the form of strands and the strands were cooled in a water bath. Subsequently, the strands were comminuted by pelletîzation.

In the second step, polymér pellets containing 1% or 5% by weight of UV stabilizer were produced. To this end, 1% by weight or 5%^!by weight of the UV stabilizer and 99% or 95% by weight, respectively, of polypropylene (Metocen® HM562S, LyondelIBasell, Rotterdam,

Netherlands) were mixed ir the extruder. All the materials were supplied in solid form to the

-30feed zone of the extruder. Ttje mixture emerged from the extruder in the form of strands and the strands were cooled in a water bath. Subsequently, the strands were comminuted by pelletization.

In the third step, the two previously produced pellet products comprising deltamethrin or UV stabilizer were mixed with pdlypropylene in the extruder such that a nominal concentration of

1% by weight of deltamethijin and a 0.2%_fby weight concentration of UV stabilizer were obtained (TK1). To this end,: 50% ofthe pellet product comprising deltamethrin, 20% or 4% of the pellet product comprising UV stabilizer and, respectîvely, 30% or 46% polypropylene were mixed in a tumble mjxer and this mixture was extruded using a corotating close10 meshing twin-screw extruder under the abovementioned conditions. The pellet mixture was supplied in solid form to the feed zone of the extruder. The mixture emerged from the extruder in the form of strands and the strands were cooled in a water bath. Subsequently, the strands were comminutetl by pelletization. The pellets contained about 0.9% by weight of deltamethrin.

i '.

The polymeric material ofithe présent inverition.iwas used to produce films having a thickness of about 50 pm. To this end, the polymeric material was initially dried at 30°C for 4 to 17 h. Subsequently, it was melted in a single-screw extruder and extruded through a film slot die. The température of the single-screw extruder was varied between 220 and 250°C. The extruded films were withdrawn using a polishing stack. The température of the first roll j J ;

of the polishing stack was about 85°C and the teitiperature of the second roll of the polishing stack was about 60°C.

The following UV stabilizers were used în the tests:

I

Table 6: UV stabilîzers

Trade name

Manufacturing company

Chemical class

Chimasorb®

BASF (Ciba), Ludwigshafen, Germany

1,6-Hexanediamine, N,N*2020 bis(2,2,6,6-tetramethyl-4piperidinyl) polymer with 2,4,6trichloro-fiS.S-triazine, reaction products with N-butyl1-butanamine and N-butyl2,2,6,6-tetramethyl-4-(CAS 192268-64-7)piperidinamine

Tinuvin® 326

BASF (Ciba), Ludwigshafen, Germany

Bumetrizole, 2-(5-chloro-2Hbenzotriazole-2-yl)-6-(1,1dimethylethyl)-4-methylphenol (CAS 3896-11-5)

Tinuvin® 571 FF

BASF (Ciba), Ludwigshafen, Germany

Triazine compound, phénol, 2(2H-benzotriazol-2-yl)-6 dodecyl-4-methyl-, branched and linear (CAS 125304-04-3)

Tinuvin® 783

BASF (Ciba), Ludwigshafen, Germany

Poly[[6-[(1,1,3,3-tetramethylFDL butyl)amino]-1,3,5-triazin-2,4diyl][(2_]2,6,6-tetramethyl-4piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl4-piperidinyl)imino]]), (CAS 71878-19-8), butanedioîc acid, dimethylester, polymer with 4hydroxy-2,2,6,6-tetramethyl-1 piperidine éthanol (CAS 65447-77-0)

The films were subsequently analysed for their deltamethrin content using the abovementioned analytical methods:

I

-32Table 7: R-a-isomer cpntent

UV stabilizer	Extrusion température	Deltamethrin (DLT) content	R-D-isomer content
	[’C]	[% by weight]	[% of DLT]
Chimasorb® 2020	220	0.859	9.989
Chimasorb® 2020	240	0.883	12.503
Chimasorb® 2020	250	0.888	14.496
Tinuvin® 326	220	0.986	0.785
Tinuvin® 326	240	0.979	0.000
Tinuvin® 326	250	0.931	0.868
Tinuvin® NOR 371 FF!	i 220	0.879	2.471
Tinuvin® NOR 371 FF	240	0.906	3.713
Tinuvin® NOR 371 FF	250	0.944	4.677
Tinuvin® 783 FDL	i 220	0.871	8.999
Tinuvin® 783 FDL	. 240	0.861	10.858
Tinuvin® 783 FDL	250	0.882	12.154

The results show that no stqrically hindered amines may be used for UV stabilization in order that an isomerization of more than 10% of the deltamethrin may be prevented in the course 5 of the further processing of the polymeric materials ofthe présent invention.

i

7th example: Prior art: coated PET nets i

The insecticide-laden Permanet net from Vestergaard Frandsen S.A., Switzerland was evaluated with respect to biologieal activity and deltamethrin content. This was followed by repeated performance of the washing procedure according to the WHOPES protocol and 10 further évaluations of biologieal activity and deltamethrin loss.

The deltamethrin content of the net was determined in the same way as described for the polypropyiene net. I i

J

-33 i

Table 8: Deltamethrin content and rétention index

Number of washes to WHOPES protocol H	Knock-down after 60 min	Mortality after 24 h	Deltamethrin (DLT) content [% by weight]	Rétention index [-]
0	100	100	0.208	0
5	100	100	0.086	84%
10	98	100	0.066	89%
15	97	84	0.059	92%
20	84	72	0.050	93%
25	69	64	0.040	94%
30	70 I	61	0.042	95%

The insecticide-laden Permanet net from Vestergaard Frandsen S.A., Switzerland was tested for active-ingredient stability after 2 weeks’ storage at 54°C. These storage conditions 5 are used to simulate a minimum shelf life of 2 years. The samples were stored at 54°C for 2 i weeks and subsequently analysed for their deltamethrin R-a-isomer content in accordance with the method described above, A double détermination was carried out.

Table 9:

R-n-isomer content

R-n-isomer of DLT i
Before 2 weeks' storage :at 54°C i	After 2 weeks’ storage at 54°C
3,35% |	47.44%
3.51% i	35.35%

The results show that this commercially available- net meets the WHO requirements in respect of knock-down and mortality for 15 washes only and has a rétention index of less than 95% after 5 washes. Furthermore, the R-ü-isomer content after 2 weeks’ storage at

54°C is distinctly more than 30%.

-348th example: Prior art: PE nets

The insecticide-laden nets Netprotect® (BESTNET EUROPE LTD., Britain) and Duranet® (Clarke Products, USA) were evaluated with respect to biological activity. This was followed by repeated performance of the washing procedure to the WHOPES protocol and further évaluations of biological activity.

.<·.,

Table 10: Biological activity

Number of washes to WHOPES protocol [-]	l Netprotect®	Duranet®
Knock-down after 60 min [%]	Mortality after 24 h [%]	Knock-down after 60 min [%]	Mortality after 24 h [%]
0	100	100	100	100
5	93	83	100	98
10	66	44	100	98
15	19	57' '	95	95
20	7	14 ;	64	70
25	n.d.	n.d. ‘	64	70
30	n.d.	n.d.	51	51
35	n.d.	n.d..	41	41

n.d. = not determined.

The results clearly show that the commercially available nets tested, which are based on polyethylene as fibre material, no longer meet the WHOPES directive in respect of biological 10 activity after distinctly fewerithan 35 washes.

Claims (8)

1. Insecticide-containing polymeric material containing deltamethrin and also a UV stabiliser, characterized in that the material includes a less than 10% R-a-isomer i fraction of the deltarriethrin, : ;

I

2. Insecticide-containing polymeric material according to Claim 1, characterized in that the material is polypropylene or polypropylene copolymer, i

I

3. Insecticide-containirig polymeric material·according to Claim 2, characterized in that the polypropylene is! produced using metallocenes as catalyst.

4.

Process for producing the insecticide-containing polymeric material according to any of Claims 1 to 3, characterized in that first the polymer to be used, deltamethrin and also a UV stabilizèr and optionally further insecticides or additives are melted together or separately at températures between 120 and 250°C and subsequently the cooling and sblidifying of the polymeric mixture takes place and also the subdivision of the laitier into pellets. ₁

I

Process according to Claim 4, characterized in that sterically unhindered compounds are used as UV staUizers.

6. Pellets containing the insecticide-containing polymeric material according to any of Claims 1 to 3, ¹ j .. .·

7. Process for produéing filaments, fibres, threads and/or yarns, characterized in that the insecticide-containing polymeric material according to any of Claims 1 to 3 or pellets according to Claim 6 is/are initially melted, formed into spun threads and cooled, and the spun threads obtained are led through a drawing system and drawn,

8. Process according! to Claim 7, characterized in that a spin finish is used in the course ofthe spinning opération.

9. Use of the insectiçide-containing polymeric materials according to any of Claims 1 to 3 or pellets according to Claim 6 in the manufacture of foils, air-cushioning materials, films, profiles, sheets, wires, threads, tapes, cable and pipe linings and casings for electrical instruments.