WO2005044001A2

WO2005044001A2 - Insecticidal composition with use indicator

Info

Publication number: WO2005044001A2
Application number: PCT/EP2004/011984
Authority: WO
Inventors: Heinz Pudleiner; Mike Dirk Bublitz; Rolf Jung
Original assignee: S. C. Johnson & Son, Inc.
Priority date: 2003-10-22
Filing date: 2004-10-22
Publication date: 2005-05-19
Also published as: WO2005044001A3

Abstract

The invention relates to an insecticidal composition with use indicator which contains one or more thermoplastically processable (co)polymers, one or more insecticidal active substances, one or more inorganic additives, one or more thermochromic substances and one or more additions from the group of the stabilizers, colourants, fragrances, organic and inorganic adjuvants, where the insecticidal active substance, the inorganic additive and the other additives are embedded in the (co)polymer; methods for its preparation and its use for controlling insects, in particular those which occur in defined or enclosed spaces.

Description

Insecticidal composition with use indicator

The invention relates to an insecticidal composition with use indicator, to methods for its preparation and its use for controlling insects , in particular those which are found in defined or enclosed spaces . The novel insect icidal compos iti ons according to the invention are characterized in that they contain one or more thermoplastically processable ( co ) polymers , one or more insecticidal act ive substances , one or more inorgani c addit ive s , one or more thermochromi c substances and one or more additions from the group of the stabilizers , colourants , fragrances , organic and inorganic adj uvants , where the insecticidal active substance , the inorganic addit ive and the other additives are embedded in the (co ) polymer . Owing to the fact that they contain thermochromic substances , they are capabl e of indi cat ing clearly the use and consumpt ion of an insecticidal compos it ion with reference to the changes of the external appearance, in particular its colour, at a specific temperature over a specific period . The invention furthermore relates to a method for its preparation and its use for controlling insects , in particular those which occur in defined or enclosed spaces .

Insecticidal compositions which consist of polymers and insect icidal active substances , where individual colourants or colourant mixtures are incorporated in the polymer matrix in order to impart an attractive appearance to the product are already known .

Also known are use indicator systems which contain a colourant or colourant mixture which is dissolved in an insecticide-containing solution and which, in the form of a coloured solution, has been applied to a pulp board or cotton board, asbestos or ceramic matrix by impregnation and which, when used in the form of insecticide tablets in combination with a suitable vapourizer-heater at a temperature of betv/een 120 and 190°C, release the colouration.

Gel vapourizers where, in combination with a vapourizer-heater, the colourant or colourant mixture dissolved in the gel is vapourized together with the insecticidal active substance through _a polymer membrane are also known.

The disadvantage of the insecticide-containing polymer tablets with incorporated colourants or colourant mixtures is that their intended use results in no or only a minor visible change which might be suitable for indicating the use or usable life, or that their colouration changes too rapidly or during its production under the effect of extrusion moulding and injection moulding at high temperatures.

Another considerable disadvantage of the polymer tablet or gel vapourizers is that, owing to the vapourization of the insecticide-containing solution or gel in combination with the embedded colourants or colouranl_ mixtures, the latter recondεnsate rapidly after vapourization and form a precipitate on the vapourizer- heater or on other surfaces in the environment of the heater, thus permanently soiling them.

A further disadvantage of the prior-art tablet or σel vapourizers is that only a limited number of colourants can be used which are sufficiently stable at thc application temperatures, sufficiently soluble in the polymer matrix and have toxicological properties which permit their use in insecticide-containing tablet or gel vapourizers. Finally, another disadvantage of a vapourizer system is that the vapourization characteristic is irregular and inhomogeneous so that an accurate and reliable statement on the duration, of the intended use of the insecticide vapourizer tablets or gels is not possible.

Another important aspect regarding the production of_. the tablet and gel vapourizers is that the switch to noncoloured variants or variants in a different colour is technically complex and requires expensive cleaninσ steps which are undesirable ecologically and economically .

It v/as therefore an object of the present invention to provide novel insecticidal compositions which have an improved insecticidal activity against insects v_/hich by preference, occur in defined or enclosed spaces, specifically midges, flies and mosquitoes, and which are simultaneously capable of reliably and clearly indicating the use and the useful life of this insecticidal composition as related to time and temperature so that insecticide-active-substance- depleted vapourizer tablets or gels can be replaced in good time by new vapourizer tablets or gels.

Surprisingly, it has now been found that this object can be achieved in accordance with the invention by novel insecticidal compositions which contain the abovementioned specific components v/hich are described hereinbelow in greater detail and whose surfaces are partially or completely impregnated or coated with specific thermochromic substances which, owing to their changes as related to temperature and time are capable of reliably and clearly indicating the use and the useful life of the insecticidal compositions in the vapourizer-heaters v/hich are suitable for this purpose. According to a first aspect, the invention relates to insecticidal compositions which are characterized in that they contain one or more thermoplastically processable (co) polymers, one or more insecticidal active substances, one or more inorganic additives, one or more thermochromic substances and one or more additions from the group of the stabilizers, colourants, fragrances, organic and inorganic adjuvants.

Preferred embodiments of the compositions according to the invention are characterized in that they contain, as insecticidal active substance ( s ) , one or more pyrethroid insecticides selected from the following group:

3-allyl-2-methylcyclopent-2-en-4-on-l-yl d/l-cis/ trans-chrysanthemate (allethrin / Pynamin ®) , 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-cis/ trans-chrysanthemate (Pynamin forte ®) , 3-allyl-2-methylcyclopent-2-en-4-on-l-yl-d-trans- chrysanthemate (Bioallethrin ®) , 2, 3, 5, 6-tetrafluorobenzyl ( + ) -lR-trans-2, 2- dimethyl-3- (2, 2-dichlorovinyl) cyclopropane- carboxylate (transf luthrin, Bayothrin ®) and (S) -2-methyl-4-oxo-3- (2-propinyl) cylopent-2-enyl (IR) -cis, trans-chrysanthemate (ETOC ®) ,

which especially preferably comprise, as insecticidal active substance, 2, 3 , 5, ^β-tetraf luorobenzyl (+)-l-R- trans-2 , 2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropane- carboxylate ( transf luthrin, Bayothrin ®) and/or 3- allyl-2-methyl-cyclopent-2-en-4-on-l-yl d-cis/trans- chrysanthemate (Pynamin forte ®)

The insecticidal compositions according to the invention preferably contain, as (co) polymer (s) , one or more am_orphous and/or partially crystalline ₍co₎ po_lymers which are thermoplastically processable an_d w_hos_e softening point is below the boiling point of t_he insecticidal active substance (s) under atmospheric pressure, t_hey _particularly preferably contain at least one ₍c_{o) pol}ymer with a. crystallite melting range of between ₁₀₀ an_{d 30}0°C, by preference between 150 and 200°C, _particu_larly preferably between 150 and 200°C.

_The in_secti_cidal compositions of the invention contain, _{as (co) pol}ymer (s) , in particular PVC (plast icized) , _polystyr_en_e, styrene/butadiene, styrene/ acrylonitrile, _acry_lonitri_le/_butadiene/styrene, polymethyl acrylate, _am_or_phou_s polycycloolef ins, cellulose esters, aromatic _poly_car_bonates, amorphous aromatic polyamides, _polyphen_ylene ethers, poly(ether) sulphones, _polyimi_des, polyethylene, polypropylene, polybutylene, _polym_et_hylpentene, PVC (unplasticized) , polyamides, _poly_et_her amides, polyester amides, polyoxymethylene, _polyet_hylene terephthalate, polybutylene terephthalate, _polyimi_des, polyether (ether) ketones and _polyur_et_hanes , blends of polycarbonates and _polybut_ylene terephthalate, blends of polyamide-6 and _styrene/_acr_ylonitrile, blends of polypropylene and _polym_et_hylpentene, or mixtures of the abovementioned polymers .

_Ver_{y e}s_pecially preferably they contain, as (co)- _po_lym_er (s), blends of polycarbonates and polybutylene tere_pht_ha_late, blends of polyamide and acrylonitrile/ _but_adi_ene/styrene with • polypropylene, blends of c_opolyesters and polypropylene, blends of polypropylene an_{d pol}ym_et_hylpentene, in particular blends of copoly- _est_ers or polyamide and acrylonitrile/butadiene/styrene wit_{h p}o_lypropylene, and mixtures of these.

_The inse_cticidal compositions according to the invention _contain by preference, as additive (s), one or more modifier(s) and/or filler(s) and reinforcing materials and/or processing auxiliaries, in particular those from the group of the nucleating agents, plasticizers, mould-release agents, flame retardants, impact rectifiers, stabilizers, in particular antioxidants, and other additives conventionally used in the field of thermoplastics, either individually or in the form of any mixture of these.

The insecticidal compositions according to the invention contain, as filler(s) and reinforcing material (s) , by preference one or more minerals, by preference those from the group consisting of gypsum, lime, glass fibre,- sand and/or natural materials, by preference those from the group consisting of starch and modified starch, cellulose, cellulose derivatives, cellulose products, wood meal and/or natural fibres, in particular those from the group consisting of hemp, flax, sisal, oilseed rape and ramie.

As thermochromic substance ( s ) , the insecticidal compositions according to the invention by preference contain one or more commercially available thermochromic lacquer from Halgret [sic] , by preference the types MC 233, MC 104-2, MC 135-2, MC 150-12, MC 153-14, MC 160-2x, MC 165-2, SC 48, SC 80, SC 155 and SC 275.

As antioxidant ( s ) , the insecticidal compositions according to the invention by preference contain one or more UV absorber (s), by preference one or more phenol derivatives, in particular those from the group butylhydroxytoluene (BHT) and butylhydroxyanisole

(BHA) , bisphenol derivatives, arylamines, in particular those from the group phenyl-α-naphthylamine and phenyl- β-naphthylamine, a condensate of phenetidine and acetone or benzophenones, individually or in the form of any mixture of these. As colourant (s) , the insecticidal compositions according to the invention by preference contain one or more inorganic pigments, in particular those from the group iron oxide, titanium oxide, Prussian Blue, and/or organic dyes, in particular those from the group alizarin, azo and metal phthalocyanin dyes.

The insecticidal compositions according to the invention contain the insecticidal active substance (s) by preference in an amount of from 0.1 to 80% by weight, by preference from 0.2 to 40% by weight, especially preferably from 1.0 to 20%^' by weight, based on the total weight of the insecticidal composition.

The insecticidal compositions according to the invention contain the (co) polymer ( s) by preference in an amount of from 1 to 99% by weight, by preference in an amount of from 3 to 95% by weight, in particular in an amount of from 5 to 93% by weight.

The insecticidal compositions according to the invention contain the additive (s) by preference in an amount of from 0.1 to 10% by weight, by preference from 0.5 to 8% by weight, in particular . in an amount of from 1 to 3% by weight.

The compositions according to the invention are by preference in the form of insecticide-containing polymer tablets or polymer gels for introduction into suitable vapourizer-heaters .

The insecticidal- compositions according to the invention contain the thermochromic substance (s) by preference in an amount of from 1 to 50 mg, by preference 5 to 40 mg, in particular from 10 to 25 mg, per 0.5 cm² surface area of the insecticidal composition, based on the dry weight of the insecticidal composition. The thermochromic substance (s) is/are added to the insecticidal composition by preference by impregnatin_g or coating their surface or a part thereof, using th_e above-stated amounts.

In accordance with a further aspect, the present invention relates to a method for the preparation of an insecticidal composition with the above-stated design or composition, v/hich is characterized in that, in a first step, the components of the insecticidal composition, v/ith the exception of the thermochromic component (s) , are compounded .in a conven ionally employed extruder and the resulting mixture is extruded to give an extrudate which, after cooling and comminution, is processed to give the desired insecticidal preparation, for example vapourizer tablets or vapourizer gels. Then, in a second step, the vapourizer preparation thus obtained is partially or completely surface-coated or surface-impregnated v/ith the thermochromic substance (s) using a customary method, using by preference a spraying, painting, screen printing, offset printing, ink-jet printing, dipping, tumbling method or the like, where either the entire surface of the vapourizer preparation or part- regions thereof are impregnated or coated with one or more thermochromic substance (s) to display _a colourless, plain or multi-coloured aspect.

In accordance with a third aspect, the present invention relates to the use of the insecticidal composition as described further above for controlling insects, in particular midges, flies and mosquitoes, which occur in particular in defined or enclosed internal spaces.

The combination according to the invention of the insecticidal compositions according to the invention encompasses mixtures which contain at least one type of pyrethroid insecticide, at least one polymer with a crystallite melting range of between 100 and 300°C, by preference betv/een 150 and 250°C, particularly preferably between 150 and 200°C, and^' at least one type of inorganic additive.

The softening range is confirmed in the case of amorphous thermoplastic polymers by the glass transition temperature and in the case of partially crystalline polymers by the melting temperature. Moreover, further additives such as stabilizers, colourants or fragrances, and organic or inorganic auxiliaries can be incorporated into the mixtures.

The insecticidal compositions according to the invention can be prepared for example as described in DE 19605581.4, DE 989232160.9 and DE 97904374.2.

The following are preferably used as pyrethroid active substances :

1) 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d/l-cis/ trans-chrysanthemate (allethrin / Pynamin ®) ,

2) 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-cis/ trans-chrysanthemate (Pynamin forte ®) , 3) 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-trans- chrysanthemate (Bioallethrin ®) , 4) 2 , 3 , 5 , ^β-tetraf luorobenzyl ( + ) -lR-trans-2 , 2 - dimethyl-3- (2, 2-dichlorovinyl) cyclopropane- carboxylate (transf luthrin, Bayothrin ®) and 5) (S) -2-methyl-4-oxo-3- (2-propinyl) cylopent-2-enyl (IR) -cis, trans-chrysanthemate (ETOC ®) ,

or mixtures of these active substances.

The active substances

3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-cis/trans- chrysanthe ate (Pynamin forte ®) and 2,3,5, 6-tetrafluorobenzyl ( + ) -l-Rtrans-2 , 2 -dimethyl -3- (2 , 2-dichlorovinyl) cyclopropanecarboxylate (transf luthrin) are especially preferably used. Polymeric materials v/hich are preferably used are amorphous and partially crystalline polymers an_d mixtures of the two which can be processed un_der thermoplastic conditions, i.e. as viscous melt, _an_d whose softening range is below the boiling point of t_he active substances to be incorporated under atmospheri_c pressure. The polymers are chosen for the respectiv_e active substance in such a way that the activ_e substance mixes at least partially with the polymers. The following are preferably used as suitable polymers:

PVC (plasticized) , polystyrene, styrene/buta-diene , styrene /acrylonitrile, aery Ion it rile /butadiene/ styren_e, polymethyl acrylate, amorphous polycycloolef ins , cellulose esters, aromatic polycarbonates, amorphous aromatic polyamides, polyphenylene ethers, poly(ether) sulphones, polyimides, polyethylene, polypropylene, polybutylene, polymethylpentene PVC (unplasticized) , polyamide, polyether amides, polyester amides, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyether (ether) ketone, copolyesters and polyurethanes .

Preferred mixtures are, for example: blends of polycarbonates with polybutylene terephthalate, blends of polyamide and acrylonitrile/butadiene/styrene with polypropylene, blends of copolyesters and polypropylene, blends of polypropylene and polymethylpentene.

Especially preferred are blends of copolyesters or polyamide and acrylonitrile/butadiene/styrene with polypropylene and mixtures of these. The impregnated or coated insecticidal compositions according to the invention can be stabilized with the aid of antioxidants by admixing a UV absorber to the formulation as additive, by preference prior to the impregnation or coating step. UV absorbers which can be employed are all known UV absorbers.

Those preferably employed are phenol derivatives, such as, for example, butylhydroxytoluene (BHT) , butylhydroxyanisole (BHA), bisphenol derivatives, arylamines, such as, for example, phenyl- - naphthylamine, phenyl-β-naphthylamine, a condensate of phenetidine and acetone or the like or benzophenones .

It is possible to use dyes, such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian Blue and organic dyes, such as, for example, alizarin, azo and metal phthalocyanine dyes and micronutrients , such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Synthetic fragrances which may be added to the tablet or gel formulations according to the invention (by preference before these are impregnated or coated) are:

_Pinene, limonene and similar hydrocarbons; 3,3,5- trim_ethylcyclohexanol, linalool, geraniol, nerol, _citronellol, menthol, borneol, borneylmethoxycyclo- _hexanol, benzyl alcohol, anise alcohol, Cinnamyl _alcohol a -phenylethyl alcohol, cis-3-hexanol , t_erpineol and similar alcohols; anetholes, musk xylene, is_oeugenol, methyleugenol and similar phenols; α-amylcinnamaldehyde, anisaldehyde, n-butyraldehyde, _cuminaldehyde , cydlamenaldehyde , decylaldehyde , isobutyraldehyde, hexylaldehyde, heptylaldehyde, n- nonylaldehyde nonadienol, citral, citronellal, _hy_dr oxy ci t r one 1 la 1 , ben za ldehy de , methyl- nonylacetaldehyde, cinnamaldehyde, dodecanol, -hexyl- _cinnamaldehyde, undecanal, heliotropin, vanillin, ethylvanillin and similar aldehydes, methyl amyl ketone, methyl α-naphthyl ketone, methyl nonyl ketone, musk ketone, diacetyl, acetylpropionyl, acetylbutyryl, carvone, methone, camphor, acetophenone, _p- methylacetophenone, ionone, methylionone and similar ketones; amylbutyrolactone, diphenyl oxide, methyl phenylglycidate, nonylacetone, coumarin, cineol, ethyl- methylphenyl glycidate and similar lactones or oxi_des, methyl formate, isopropyl formate, linalyl forma_te, ethyl acetate, octyl acetate, methyl acetate, benzy_l acetate, cinnamyl acetate, butyl propionate, isoamy_l acetate, isopropyl isobutyrate, geranyl isovalerate, allyl caproate, butyl heptylate, octyl carprylat_e, methyl heptinecarboxyiate, methyl octinecarboxylate, isoamyl carprylate, methyl laurate, ethyl myristat_e, methyl myristate, ethyl benzoate, benzyl benzoat_e, methylcarbinylphenyl acetate, isobutylphenyl acetat_e, methyl cinna ate, styracin, methyl salicylate, et_hy_l anisate, methyl anthranilate, ethyl pyruvate, ethyl - butyl butyrate, benzyl propionate, butyl acetate, buty_l butyrate, p-tert-butylcyclohexyl acetate, dery_l acetate, citronellyl acetate, citronellyl formate, _p- cresyl acetate, ethyl butyrate, ethyl caproate, ethy_l cinnamate, ethyl phenylacetate, ethylene brassylate, geranyl acetate, geranyl formate, isoamyl salicylat_e, isoamyl valerate, isobornyl acetate, linalyl acetat_e,

methyl anthranilate, methyl dihydro j asmonate, nony_l acetate, α-phenylethyl acetate, t richloromethylene phenylcarbinylacetate , terpinyl acetate, vetiver_yl acetate and similar esters.

In' general, the compositions contain between 0.1 an_d 80%, by preference between 0.2 and 40%, especial_ly preferably between 1.0 and 20%, of active substance.

The following can be used as additives: modifier_s and/or fillers and reinforcing materials and/_or processing auxiliaries such as, for example, nucleati_ng agents, plasticizers , mould-release agents, flame retardants, impact rectifiers, stabilizers, or additives which are otherwise conventionally used in the field of thermoplastics..

The following can be used as preferred fillers and reinforcing materials: minerals such as, for example, gypsum, lime, glass fibre, sand and/or natural materials, such as, for example, starches and modified starches, cellulose, cellulose derivatives, cellulose products, wood meal or natural fibres, such as, for example, hemp, flax, sisal, oilseed rape or ramie.

Thermochromic substances which can preferably be used are commercially available thermochromic lacquers from Kallcrest such as, for example, the following types of thermochromic lacquers: MC 233, MC 104-2, MC 135-2, MC 150-12, MC 153-14, MC 160-2x, MC 165-2, SC 48, SC 80, SC 155, SC 275.

The preparation and use of the compositions according to the invention can be seen from the examples which follow:

• A variety of methods can be. employed for impregnating or coating the tablet or gel products with the thermochromic substances: for example spraying, painting, screen printing, offset printing, ink-jet printing, dipping and tumbling methods.

The part-regions of the surface to be coated or else the entire surface can be impregnated or coated to give a colourless, plain or multi-coloured aspect. Example 1 Compounding active substances into various polymers

Compounding was done using a BRABEMDER PLASTICORDER PL 2000 twin-screw metering extruder (extruder type: 35/17 D, extruder cooling: air, inlet cooling: water, 3 mm round extruder die, four electrically heated heating zones ) . The polymer granules are etered into the extruder at the respective temperature via an Engelhardt balance. The active substance is warmed in a storage container heated with steam and added using a gear pump ₍Ismatec) . The throughput is adjusted to a total of 6 kg/h.

The polymer extrudate which is discharged is cooled in a water bath and then comminuted in the granulator. The granules are dried at about 50°C in a water pump vacuum.

Examples: polymer vapourizers

* TPX RT 31 polymethylpentene * * pp polypropylene Example 1: Plain coating with thermochromic substances

Support : Insecticide-containing polymer tablet

No TPX RT 31 84.0 polypropylene 13.5 active substance 1.3 additives 1.0 colour/ ntioxidant 0.2

Coating (thermochromic substance]

MC 135 Lacquer fro 15 mg on 0.5 cm²" Hallcrest [sic] Sample preparation

A defined amount of thermochromic substance (MC 135) is pipetted onto the surface. The slightly viscous substance is distributed using a spatula. The product is then dried over 24 hours at room temperature (approx. 2 ^CC)

Test report

Vapourization of in each case three samples usinα

Baygon Mat heater PV 3 at 145 - 152°C over 12 hours.

Sampling was carried out after each vapourization period of 4 hours.

Result use indicator

The colour of the area coated with the thermochromic substance (MC 135) changes after as little as 4 hours from initially pink to dark purple. Result biological activity

" calculated means, data based on linear regression * kd after the end of the test (in the present case 12 h) and dead insects 24 hours after starting the heating device Example 2 Plain coating with thermochromic substance MC 104

Support : Insecticide-containing polymer tablet

Mo. TPX RT 31 84.0 polypropylene 13.5 active substance 1.3 additives 1.0 colour/antioxidant 0.2

Coatinσ

MC 104-2 Lacσuer from 15 mg on 0.5 cm Hallcrest Sample preparation

A defined amount of thermochromic substance (MC104) is pipetted onto the surface. The slightly viscous substance is distributed using a spatula. The product is then dried over 24 hours at room temperature (approx. 23^CC)

Test report

Vapourization of in each case three samples using Baygon Mat heater PV 3 at 145 - 152°C over 12 hours. Sampling was carried out after each vapourization period of 4 hours.

Result use indicator

The colour of the area coated with the thermochromic substance changes after 12 hours from initially pale green to σrey. Result biological activity

Polymer ma: Eaygon polymer mat

Example 2 Standard without coatmc

Treated Kd effect rα efzect insects kd Dead ter hour hours nd r.o rs a.-.d ir.seccs minutes 50 35' 5c' 100 ICC 100 24' 5S' ICC 100 IOC 30' 53' 1C0 100 1C0 23' lh!3' 100 l 00' 100 100 23' lh35' 100 31' lhlS' 100 100 33' ln22' 100 100 3c' lr.31' 100 100 33' ln31' 100 100 45' lh54' 100 100 34' lh.33' 100 100 33' lh40' 100 100 32' lhl9' 100 100 lh25' 100 100 9 33' lhl4' 100 lh36' 99 100 10 30' 100 lh!2' 97 100 40' FΞ Example 3: Multi-coloured coating with two thermochromic substances

Support : Insecticide-containing polymer tablet

Coating

Sample preparation

A defined amount of the two thermochromic substances is pipetted onto the respective parts of the surface. The slightly viscous substance is distributed using a spatula. The product is then dried over 24 hours at room temperature (approx. 23°C)

Test report Vapourization of in each case three samples using Baygon Mat heater PV 3 at 145 - 152°C over 12 hours. Sampling v/as carried out after each vapourization period of 4 hours.

Result use indicator

The colour of the thermochromic substance on the riαht part changes after 4 hours from green to black.

The colour of the thermochromic substance on the left part changes after 12 hours from pale green to grey.

L t ^S Tcr

Claims

Patent Claims

1. Insecticidal composition, characterized in that it contains one or more thermoplastically processable (co) polymers, one or more insecticidal active substances, one or more inorganic additives, one or more thermochromic substances and one or more additions from the group of the stabilizers colourants; fragrances, organic and inorganic adj uvants .

2. Insecticidal composition according to Claim 1 characterized in that it contains, as insecticidal active subs tance ( s ) , one or more pyrethroid insecticides selected from the following group:

3-allyl-2-methylcyclopent-2-en-4-on-l-yl-d/l-cis/ trans chrysanthemate (allethrin / Pynamin ®) , 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-cis/ trans-chrysanthemate (Pynamin forte ®) , 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-trans- chrysanthemate (Bioallethrin ®) , 2, 3, 5, 6-tetrafluorobenzyl (÷) -lR-trans-2,2- dimethyl-3- (2, 2-dichlorovinyl) cyclopropane- carboxylate (transfluthrin, Bayothrin ®) and (S) -2-methyl-4-oxo-3- (2-propinyl) cylopent-2-enyl (IR) -cis, trans-chrysanthemate (ETOC ®) .

3. Insecticidal composition according to Claim 2, characterized in that it contains, as insecticidal active substance, 2 , 3 , 5, ^β-tetrafluorobenzyl ( + ) - lR-trans-2, 2-dimethyl-3- (2, 2- dichlorovinyl) eyelopropanecarboxylate (transfluthrin, Bayothrin ^®) and/or 3-allyl-2- methylcyclopent-2-en-4-on-l-yl d-cis /trans- chrysanthemate (Pynamin forte ®) .

4. Insecticidal composition according to at least one of Claims 1 to 3, characterized in that it contains, as (co) polymer (s ) , one^'or more amorphous and/or partially crystalline (co)poly ers which are thermoplastically processable and whose softening point is below the boiling point of the insecticidal active substance (s) under atmospheric pressure . 5. Insecticidal composition according to Claim 4, characterized in tha^'t it . contains at least one ( co ) polymer with a crystallite melting range of between 100 and 300°C, by preference between 150 and 200°C, particularly preferably between 150 and 200°C.

6. Insecticidal composition according to at least one of Claims 1 to 5, characterized in that it contains, as (co) polymer ( s ) , PVC (plas ticized) , polystyrene, s t yrene /bu t adi e ne , styrene/ acrylonitrile, acrylonitrile/butadiene/st yrene, polymethyl acrylate, amorphous polycycloolef ins , cellulose esters, aromatic polycarbonates, amorphous aromatic polyamides, polyphenylene ethers, poly(ether) sulphones, polyimides, polyethylene, polypropylene, polybutylene, polymethylpentene, PVC ( unp 1 a s t i c i z ed ) , polyamides, polyether amides, polyester amides, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyimides, polyether (ether) ketones and polyurethanes , blends of polycarbonates and polybutylene terephthalate, blends of polyamide-6 and styrene/acrylonitrile, blends of polypropylene and polymethylpentene, or mixtures of the abovementioned polymers.

7. Insecticidal composition according to Claim 6, characterized in that it contains, as (co) polymer (s ) , blends of polycarbonates and polybutylene terephthalate, blends of polyamide and acrylonitrile/butadiene/styrene with polypropylene, blends of copolyesters and polypropylene, blends of polypropylene and polymethylpentene, in particular blends of copolyesters or polyamide and acrylonitrile/ butadiene/styrene with polypropylene, and mixtures of these. δ. Insecticidal composition .according to at least 'one of Claims 1 to 7, characterized in tha_t it contains, as additive (s) , one or more modifier (s) and/or filler (s) and reinforcing materials and/or processing auxiliaries, in particular those from the group of the nucleating agents, plastici∑ers, mould-release agents, flame retardants, impact rectifiers, stabilizers, in particular antioxidants, and other additives conventionally used in the field of thermoplastics, either individually or in the form of any mixture of these .

9. Insecticidal composition according to Claim 8, characterized in that it contains, as filler(s) and reinforcing material (s), one or more minerals, by preference those from the group consisting of gypsum, lime, glass fibre, sand and/or natural materials, by preference those from the group consisting of starch and modified starch, cellulose, cellulose derivatives, cellulose products, wood meal and/or natural fibres, in particular those from the group consisting of hemp, flax, sisal, oilseed rape and ramie.

10. Insecticidal composition according to at least one of Claims 1 to 9, characterized in that it contains, as temperature-sensitive substance (s) , one or more commercially available thermochromic lacquer from Halgret [sic], preferably the types MC 233, MC 104-2, MC 135-2, MC 150-12, MC 153-14, MC 160-2x, MC 165-2, SC 48, SC 80, SC 155 and SC 275. 11. Insecticidal composition according to at least one of Claims 1 to 10, characterized in that it contains as antioxidant, one or more UV absorber (s), by preference one or more phenol derivatives, in particular those from the grou_p butylhydroxytoluene ⁽BHT) and butylhydroxyanisole ⁽BHA⁾, bisphenol derivatives, arylamines, in particular those from the group phenyl-α- naphthylamine and phenyl-β-napht hyla ine, a condensate of phenetidine and acetone or benzophenones, individually or in the form of any mixture of these.

12. Insecticidal composition according to at least one of Claims 1 to 11, characterized in that it contains, as colourant (s ) , one or more inorganic pigments, in particular those from the group iron oxide, titanium oxide, Prussian Blue, and/or organic dyestuffs, in particular those from the group alizarin, azo and metal phthalocyanin dyestuffs .

13. Insecticidal composition according to at least one of Claims 1 to 12, characterized in that it contains the insecticidal active substance in an amount of from 0.1 to 80% by weight, by preference from 0.2 to 40% by weight, especially preferably from 1.0 to 20% by weight, based on the total weight of the insecticidal composition.

14. Insecticidal composition according to at least one of Claims 1 to 13, characterized in that it contains the (co) polymer (s) in an amount of from 1 to 99% by weight, by preference in an amount of from 3 to 95% by weight, in particular in an amount of from 5 to 93% by weight. 15. Insecticidal composition according to at least one of- Claims 1 to 14, characterized in that it contains the additive (s) in an amount of from 0.1 to 10% by weight, by preference from 0.5 to 8% by weight, in particular in an amount of from 1 to 3% by weight. 16. Insecticidal composition according to at least one of Claims 1 to 15, characterized in that it is in the form of an insecticide-containing oolvmer tablet or polymer gel for introduction in_to a suitable vapourizer-heater.

17. Insecticidal composition according to at least one of Claims 1 to 16, characterized in tha_t i_t contains the thermochromic substance (s) in an amount of from 1 to 50 mg, by preference 5 to 40 mg, in particular from 10 to 25 mg, per 0.5 cm² surface area of the insecticidal composition, based on the dry weight of the insecticidal composition .

18. Insecticidal composition according to Claim 17, characterized in that it is partially or completely surface-impregnated and/or surface- coated v/ith the thermochromic substance (s) to provide a colourless, plain or multi-coloured aspect.

19. Method for the preparation of the insecticidal composition according to one of Claims 1 to 18, characterized in that,- in a first step, the components of the insecticidal composition, with the exception of the thermochromic substance (s) , are compounded in an extruder -and the resulting mixture is extruded to give an extrudate which is then cooled, comminuted and processed to give a product for vapourization, in particular a vapourizer tablet or vapourizer gel, which is then, in a second step, partially or completely surface-impregnated and/or surface-treated in a manner known per se v/ith the thermochromic substance (s) to provide a colourless, plain or multi-coloured aspect.

20. Use of the insecticidal composition accordinσ to one of Claims 1 to 19 fqr controlling insects, in particular midges, flies and mosquitoes, v_/hich occur by preference in defined or enclosed internal spaces.

21. An insecticidal composition according to at least one of claims 1 to 18 with use indicator for controlling insects ⁱn defined or enclosed spaces, in the form of vapourizer tablets or gels, based on thermoplastic polymers, the insecticidal composition comprising a) one or more thermoplastically processable (co) polymers , b) one or more insecticidal active substances, c) one or more inorganic additives, d) one or more additions from the group of the stabilizers, colourants, fragrances, organic and inorganic adjuvants, and e) one or more thermochromic substances, wherein components (b) ^' to (d) are embedded in component (a) and component (e) is present in the form of a surface-layer or surface-impregnation

22. The insecticidal composition according to Claim 21 characterized in that it contains, as insecticidal ' active substance (s), one or more pyrethroid insecticides selected from the following group: 3-allyl-2-methylcyclopent-2-en-4-on-l-yl-d/l-cis/ trans chrysanthemate (allethrin / Pynamin ^®) , 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d-cis/ trans- chrysanthemate (Pynamin forte ^®) , 3-allyl-2-methylcyclopent-2-en-4-on-l-yl d- trans- chrysanthemate (Bioallethrin^®) , 2,3,5, 6-tetrafluorobenzyl (+) -IR-trans -2 , 2 -dimethyl -3 - (2 , 2-dichlorovinyl) -cyclopropane-carboxylate (transfluthrin, Bayothrin ^®) and (S) -2-methyl-4-oxo-3- (2 -propinyl ) cylopent-2 -enyl (IR) - cis, trans-chrysanthemate (ETOC ^®) .

23. The insecticidal composition according to Claim 21, characterized in that it contains, as insecticidal active substance (s) , 2,3,5, 6-tetrafluorobenzyl (+ ) IR-trans -2 , 2 -dimethyl -3 - (2,2- dichlorovinyl) cyclopropanecarboxylate (transfluthrin, Bayothrin ^® and/or 3-allyl-2methylcyclopent-2-en-4-on-l-yl d-cis/trans- chrysanthemate (Pynamin forte ^®) .

24. The insecticidal composition according to at least one of Claims 21 to 23, characterized in that it contains, as (co) polymer (s) , one or more amorphous and/or partially crystalline (co) polymers which are thermoplastically processable and whose softening point is below the boiling point of the insecticidal active substance (s) under atmospheric pressure.

25. The insecticidal composition according to Claim 24, characterized in that it contains at least one (co) polymer with a crystallite melting range of between 100 and 300^°C, by preference between 150 and 200^°C, particularly preferably between 150 and 200°C. 26 The insecticidal composition according to at least one of Claims 21 to 25, characterized in that it contains, as (co) polymer (s) , PVC (plasticized) , polystyrene, styrene/butadiene, styrene/ acrylonitrile, acryloni- trile/butadiene/styrene, polymethyl acrylate, amor^¬ phous polycycloolefins, cellulose esters, aromatic polycarbonates, amorphous aromatic polyamides, polyphenylene ethers, poly (ether) sulphones, poly^¬ imides, polyethylene, polypropylene, polybutylene, po^¬ lymethylpentene, PVC (unplasticized) , polyamides, polyether amides, polyester amides, polyoxymethylene, polyethylene terephthalate, polybutylene terephtha^¬ late, polyimides, polyether (ether) ketones and polyu- rethanes, blends of polycarbonates and polybutylene terephthalate, blends of polyamide-6 and styrene/- acrylonitrile, blends of polypropylene and poly^¬ methylpentene, or mixtures of the abovementioned poly^¬ mers . 7 The insecticidal composition according to Claim 26, characterized in that it contains, as (co⁾polymer ⁽s⁾ , blends of polycarbonates and polybutylene terephtha^¬ late, blends of polyamide and acrylonitrile/buta- diene/styrene with polypropylene, blends of copolyes^¬ ters and polypropylene, blends of polypropylene and po^¬ lymethylpentene, in particular blends of copolyesters of polyamide and acrylonitrile/ butadiene/styrene with polypropylene, and mixtures of these.

28. The insecticidal composition according to at least one of Claims 21 to 27, characterized in that it contains, as thermochromic substance (s) , one or more commercially available thermochromic lacquers from Halgret Company, preferably the types MC 233, MC 104-2, MC 135-2, MC 150- 12, MC 153-14, MC 160-2x, MC 165-2, SC 48, SC 80, SC 155 and SC 275.

29. The insecticidal composition according to at least one of Claims 21 to 28, characterized in that it contains, as additive (s) , one or more modifier (s) and/or filler (s) and reinforcing materials and/or processing auxiliaries, in particular those from the group of the nucleating agents, plasticizers , mould-release agents, flame retardants, impact rectifiers, stabilizers, in particular antioxidants , and other additives conventionally used in the field, of thermoplastics, either individually or in the form of any mixture of these.

30. The insecticidal composition according to Claim 29, characterized in that it contains, as filler (s) and reinforcing material (s) , one or more minerals, by preference those from the group consisting of gypsum, lime, glass fibre, sand and/or natural materials, by preference those from the group consisting of starch and modified starch, cellulose, cellulose derivatives, cellulose products, wood meal and/or natural fibres, in particular those from the group consisting of hemp, flax, sisal, oilseed rape and ramie.

31. The insecticidal composition according to at least one of Claims 21 to 30, characterized in that it contains, as antioxidant (s) , one or more UV absorber (s), by preference one or more phenol derivatives, in particular those from the group butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA) , bisphenol derivatives, aryla ines, in particular those from the group phenyl -α- naphthylamine and phenyl- (β-naphthylamine, a condensate of phenetidine and acetone or benzophenones, individually or in the form of any mixture of these.

32. The insecticidal composition according to at least one of Claims 21 to 31, characterized in that it contains, as colourant (s) , one or more inorganic pigments, in particular those from the group iron oxide, titanium oxide, Prussian Blue, and/or organic dyestuffs, in particular those from the group alizarin, azo and metal . phthalocyanin dyestuffs.

33. The insecticidal composition according to at least one of Claims 21 to 32, characterized in that it contains the insecticidal active substance in an amount of from 0.1 to 80% by weight, by preference from 0.2 to 40% by weight, especially preferably from 1.0 to 20% by weight, based on the total weight of the insecticidal composition.

34. The insecticidal composition according to at least one of Claims 21 to 33, characterized in that it contains the (co) polymer (s) in an amount of from 1 to 99% by weight, by preference^" in ^'an amount of from 3 to 95% by weight, in particular in an amount of from 5 to 93% by weigh .

35. The insecticidal composition according to at least one of Claims 21 to 34, characterized in that it contains the thermochromic substance (s) in an amount of from 1 to 5₀ mg, by preference 5 to 40 mg, in particular from 10 to 25 mg, per 0.5 cm² surface area of the insecticidal composition, based on the dry weight of the insecticidal composition.

36. The insecticidal composition according to Claim 35, characterized in that it is partially or completely surface-impregnated and/or surface-coated with the thermochromic substance (s) to provide a colourless, plain or multi-coloured aspect.

37. The insecticidal composition according to at least one of Claims 21 to 36, characterized in that it contains the additive (s) in an amount of from 0.1 to 10% by weight, by preference from 0.5 to 8% by weight, in particular in an amount of from 1 to 3% by weight.

38. The insecticidal composition according to at least one of Claims 21 to 37, characterized in that it is in the form of an insecticide-containing polymer tablet or polymer gel for introduction into a suitable vapourizer-heater.

39. A method for the preparation of the insecticidal composition according to one of Claims 21 to 38, characterized in that, in a first step, the components of the insecticidal composition, with the exception of the thermochromic substance (s) , are compounded in an extruder and the resulting mixture is extruded to give an extrudate which is then cooled, comminuted and processed to give a product for vapourization, in particular a vapourizer tablet or vapourizer gel, which is then, in a second step, partially or completely surface- impregnated and/or surface-treated in a manner known per se with the thermochromic substance (s) to provide a colourless, plain or multicoloured aspect .

₄0. Use of the insecticidal composition according to one of Claims 21 to 39 for controlling insects, in particular midges, flies and mosquitoes, which occur by preference in defined or enclosed internal spaces.