AU2006238677A1 - Aerosol insecticide composition - Google Patents

Description

WO 2006/111750 PCT/GB2006/001438 1 AEROSOL INSECTICIDE COMPOSITION TECHNICAL FIELD OF THE INVENTION The present invention provides an aerosol insecticide composition that is suitable for killing crawling and/or flying insects as well as preferably the bacteria that the insects carry or leave behind. 5 BACKGROUND OF THE INVENTION 1. Background art Insects carry surprisingly large amounts of bacteria. For example, a single fly can contaminate feed or food with enough bacteria to cause illness. Moist, warm, decaying 10 material protected from sunlight is favoured for fly eggs to hatch and in only 8 short hours for fly larvae or maggots to grow. Flies are transmitters of disease primarily because they feed on human and animal wastes. The dangerous bacteria present in these wastes stick to the mouth, footpads and hairs of flies and may then be deposited on food. Fly faeces, which contain disease-bearing organisms, can also contaminate 15 human food. And since flies have no teeth and must take their nourishment in liquid form, they spit on solid food and let it dissolve before consuming. Fly spittle, or vomitus, is swarming with bacteria and contaminates feed and areas where feed is stored. 20 Cockroaches are known to carry disease organisms such as bacteria on their bodies. The most important diseases transmitted by cockroaches in this way are gastroenteritis bacteria leading to food poisoning, dysentery and other illnesses. Any insect that feeds on blood also has the potential of transmitting disease organisms 25 from human to human. For example, mosquitoes are highly developed blood-sucking insects and are the most formidable transmitters of disease in the animal kingdom. Mosquito-borne diseases are caused by human parasites that have a stage in their life cycle that enters the blood stream. The female mosquito picks up the blood stage of the parasite when she imbibes blood to develop her eggs. The parasites generally use the 30 mosquito to complete a portion of their own life cycle and either multiply, change in form inside the mosquito or do both. After the mosquito lays her eggs, she seeks a second blood meal and transmits the fully developed parasites to the next unwitting host. Malaria is a parasitic protozoan that infects the blood cells of humans and is WO 2006/111750 PCT/GB2006/001438 2 transmitted from one human to the next by Anopheles mosquitoes. Encephalitis is a virus of the central nervous system that is passed from infected birds to humans by mosquitoes that accept birds as blood meal hosts in addition to humans. Yellow fever is a virus infection of monkeys that can either be transmitted from monkey to human or 5 from human to human in tropical areas of the world. Dog heartworm is a large filarial worm that lives in the heart of dogs but produces a blood stage small enough to develop in a mosquito. The dog heartworm parasite does not develop properly in humans and is not regarded as a human health problem. A closely related parasite, however, produces human elephantiasis in some tropical areas of the world, a debilitating mosquito-borne 10 affliction that results in grossly swollen arms, legs and genitals. The best way to reduce insect borne disease is through insect control and .personal protection. 15 2. General As used in the specification and claims, the singular form "a," "an" and "the" include plural references unless the context clearly dictates otherwise. For example, the term "an antimicrobial ingredient" includes a plurality of antimicrobial ingredients, including mixtures thereof. 20 As used herein the term "derived" or "derivative" shall be taken to indicate that a specified integer is obtained from a particular source albeit not necessarily directly from that source. 25 A "composition" is intended to mean a combination of active agent and another compound or composition, inert (for example, an excipient) or active, such as additional insecticides. Unless the context requires otherwise or specifically stated to the contrary, integers, 30 steps, or elements of the invention recited herein as singular integers, steps or elements clearly encompass both singular and plural forms of the recited integers, steps or elements. The embodiments of the invention described herein with respect to any single 35 embodiment shall be taken to apply mutatis mutandis to any other embodiment of the invention described herein.

WO 2006/111750 PCT/GB2006/001438 3 Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated step or element or integer or group of steps or elements 5 or integers but not the exclusion of any other step or element or integer or group of elements or integers. Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is to be 10 understood that the invention includes all such variations and modifications. The invention also includes all of the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations or any two or more of said steps or features. 15 The present invention is not to be limited in scope by the specific examples described herein. Functionally equivalent products, compositions and methods are clearly within the scope of the invention, as described herein. SUMMARY OF THE INVENTION 20 In work leading to the present invention, the inventors sought to provide an "all insect killer" (AIK) and a "crawling insect killer" (CIK) and/or "flying insect killer" (FIK) aerosol product that preferably kills the insect as well as a bacterium that the insect carries or leaves behind. Preferably the aerosol insecticide comprises good germ kill activity i.e. effective antibacterial activity as well as good knock-down and kill 25 capabilities for flying and/or crawling insects. It also is desirable that the aerosol insecticide composition is a single phase composition to avoid the need to agitate the product before use. The inventors have now found that excellent insecticidal activity and antibacterial 30 activity is achieved with an aerosol composition which comprises one or more synthetic pyrethroids, a Cs-C 12 alcohol, a quaternary ammonium compound, and a C

C

4 alcohol. The most preferred aerosol formulation is a single phase composition. Accordingly, in one aspect the present invention provides a non-aqueous aerosol 35 antibacterial insecticide composition comprising: a) one or more synthetic pyrethroids in a total amount of about 0.001 - 1% w/w, WO 2006/111750 PCT/GB2006/001438 4 b) one or more Cs-C 12 alcohols in a total amount of about 0.02 w/w - 20.0% w/w, c) one or more quaternary ammonium compounds in a total amount of about 0.002 - 0.5% w/w, d) one or more C 1

-C

4 alcohols in a total amount of about 0.5 - 20.0% w/w, 5 e) one or more propellants in a total amount of about 3-90% w/w, f) optionally one or more pyrethroid synergists, g) optionally one or more other insecticides and h) optionally one or more solvents. 10 The successful use of the quaternary ammonium compound together with a C1-C 4 alcohol and a Cs-C 12 alcohol in an insecticidal formula is surprising for several reasons. First, the inventors found that in the absence of water the quaternary ammonium compound requires the presence of one or more C 1

-C

4 alcohol - 0.5 - 20.0% w/w to enable the quaternary ammonium's antibacterial activity. The inventors also found, 15 however, that the presence of the C 1

-C

4 alcohol significantly depresses the insecticidal activity (measured by knockdown times) of the synthetic pyrethroid and furthermore that the presence of an amount of C 1

-C

4 alcohol may cause an insecticidal composition which also comprises a pyrethroid to split into two phases. 20 More surprisingly, the inventors found that the additional presence of a C 8

-C

1 2 alcohol 0.02 - 20.0% w/w in the aerosol composition comprising a synthetic pyrethroid, a quaternary ammonium compound, and a C 1

-C

4 alcohol effectively overcomes the detrimental effects of the C 1

-C

4 alcohol such that the composition of the present invention is preferably a single phase aerosol composition. Furthermore, the 25 composition of the present invention displays a marked improvement of its insect knockdown times i.e. its insecticidal activity, when compared to an insecticide having the same formula but which does not comprise a C 8

-C

12 alcohol. Accordingly, the Cs

C

12 alcohol acts to restore the efficacy of the synthetic pyrethroid in the aerosol insecticide composition of the present invention to provide an insecticidal composition 30 with better insecticidal activity than would otherwise be expected. The present inventors found that the activity of. the insecticide of the present invention which includes an antibacterial agent, a synthetic pyrethroid and a C 8

-C

1 2 alcohol is the same or better than a basic comparative formula (see Example 1). 35 In another preferred embodiment of the invention, the non-aqueous aerosol antibacterial insecticide composition comprises two or more synthetic pyrethroids.

WO 2006/111750 PCT/GB2006/001438 5 Accordingly, the invention preferably provides a single phase non-aqueous aerosol insecticide composition comprising a) two or more synthetic pyrethroids - in a total amount of about 0.001 - 1% w/w, b) one or more Cs-C 2 alcohols - in a total amount of about 0.02 w/w - 20.0% w/w, 5 c) one or more quaternary ammonium compounds - in a total amount of about 0.002 - 0.5% w/w, d) one or more CI-C 4 alcohols - in a total amount of about 0.5 - 20.0% w/w, e) one or more propellants - in a total amount of about 3-90% w/w, f) optionally one or more pyrethroid synergists, 10 g) optionally one or more other insecticides; and h) optionally one or more solvents. More preferably the non-aqueous aerosol antibacterial insecticide composition comprises three synthetic pyrethroids. Accordingly, the invention preferably provides 15 a single phase aerosol insecticide composition comprising a) three or more synthetic pyrethroids - in a total amount of about 0.001 - 1% w/w, b) one or more Cs-C 2 alcohols - in a total amount of about 0.02 w/w - 20.0% w/w, c) one or more quaternary ammonium compounds - in a total amount of about 0.002 - 0.5% w/w, 20 d) one or more C 1

-C

4 alcohols - in a total amount of about 0.5 - 20.0% w/w, e) one or more propellants - in a total amount of about 3-90% w/w, f) optionally one or more pyrethroid synergists, g) optionally one or more other insecticides; and h) optionally one or more solvents 25 In one embodiment the composition is suitable for use as an "all insect killer". In another embodiment the composition is suitable for use as a "crawling insect killer", and in yet another embodiment the composition is suitable for use as a "flying insect killer". 30 Preferably the aerosol composition of the present invention is suitable for direct or indirect application to an insect. For example, the aerosol composition may be sprayed at the insect to contact it directly or alternatively or in addition to this, the aerosol composition may be used as a surface spray such that the insect comes into contact with 35 a surface that has been sprayed with the aerosol composition. In another embodiment, the aerosol composition is also suitable for targeting a surface or area of insect WO 2006/111750 PCT/GB2006/001438 6 infestation, or breeding areas. Preferably, the aerosol composition is either sprayed directly at the insect or onto a contaminated surface. Accordingly, in a second aspect the invention provides a method of killing insects 5 comprising applying to said insects or to a target site of insect infestation a non aqueous aerosol insecticide composition comprising one or more synthetic pyrethroids, one or more Cs-C 12 alcohols, one or more quaternary ammonium compounds, and one or more C-C 4 alcohols, as provided in any one of the composition of the invention above. In alternate embodiments, the method comprises using a composition 10 comprising two or more or three or more synthetic pyrethroids. BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a bar graph of the efficacy results as determined by measuring the KD50 and the KD 90 of various insecticide formulas. 15 DETAILED DESCRIPTION OF THE INVENTION The aerosol insecticide composition of the present invention is preferably suitable for use both indoors and outdoors. Preferably the all insect killer insecticide composition is suitable for killing for example, flies, mosquitoes, gnats, cockroaches, and garden 20 insects. Preferably the insecticide also kills, for example, lice and louse eggs on garments and bedding, including mattresses and furniture that can neither be laundered or dry cleaned, as well as houseflies, fruit flies, wasps, hornets, bees, black flies, skipper flies, blow flies, small moths, waterbugs, palmetto bugs, silverfish, firebrats, crickets, scorpions, spiders, millipedes, centipedes, sowbugs, ants and ticks. 25 The aerosol insecticidal composition of the present invention is also preferably a single phase composition. The advantage of a single phase composition is that there is no requirement to mix the ingredients by agitation prior to use. As used herein the term single phase is understood to include micellar solutions. 30 In an alternate embodiment, the aerosol insecticidal composition of the present invention is a microemulsion. Due to the thermodynamically stable nature of a microemulsion, inherently it need not be agitated prior to use.

WO 2006/111750 PCT/GB2006/001438 7 Synthetic Pyrethroids Pyrethrins refer to a group of closely related esters extracted from the Pyrethrum flower (Chrysanthemum cinerariaefolium). These compounds are effective pesticides. Pyrethroids are any of several synthetic compounds chemically related to pyrethrin, 5 having insecticidal activity. For example permethrin is a synthetic pyrethroid useful for killing adult mosquitoes. Pyrethroids tend to have a relatively low degree of toxicity to humans and animals and hence are desirable to use for pest control. Aerosol formulations containing pyrethroids 10 have the added desirability of effectively delivering small amounts of insecticide due to the dispersion of the active ingredient and penetrating nature of an aerosol spray. According to the present invention one or more synthetic pyrethroid is present in an amount of about 0.001 - 1% w/w, more preferably about 0.01 - 0.5% w/w. 15 Preferably the one or more synthetic pyrethroid is selected from the group comprising imiprothrin, esbiothrin, d-phenothrin, tetramethrin, allethrin, prallethrin, transfluthrin, resmethrin, permethrin, cypermethrin, deltamethrin, bifenthrin, lambdacyhalothrin, cyphenothrin, cyfluthrin and metofluthrin including mixtures and isomers thereof. As 20 used in this specification, the phrase "mixtures and isomers thereof" is intended to encompass mixtures of the synthetic pyrethroids specified, isomers of the synthetic pyrethroids specified and mixtures of the of synthetic pyrethroids specified with isomers of the synthetic pyrethroids specified. In this regard, it is known in the art that many of the pyrethroids used commercially are mixtures of isomers. 25 Other insecticides or synergists include pyrethrum, dichlorvos, propoxur, and piperonyl butoxide. One preferred synthetic pyrethroid is imiprothrin. Generally, imiprothrin will be 30 incorporated in an amount of about 0.01 - 0.5% w/w, more preferably about 0.01 0.1% w/w and more preferably about 0.02% - 0.07% w/w. Another preferred synthetic pyrethroid is tetramethrin, which is preferably present in the composition in an amount of about 0.01 - 0.5% w/w.

WO 2006/111750 PCT/GB2006/001438 8 Synthetic pyrethroids such as esbiothrin will generally be incorporated in an amount of about 0.01 - 0.5% w/w, more preferably about 0.10 - 0.3% w/w and most preferably about 0.12% w/w. 5 Other synthetic pyrethroids cypermethrin and permethrin will generally be incorporated to give a concentration of about 0.2 - 0.4% w/w. D-phenothrin is preferably present in an amount of about 0.01 - 0.15% w/w, more preferably about 0.02 - 0.1% w/w and most preferably about 0.03% w/w. 10 In another preferred embodiment of the invention, the composition comprises two or more synthetic pyrethroids. Most preferably the two or more synthetic pyrethroids are selected from the group 15 comprising imiprothrin, esbiothrin, d-phenothrin and cypermethrin. Most preferably the composition comprises imiprothrin - 0.01 - 0.1% w/w, and d-phenothrin 0.01 0.15% w/w, or imiprothrin 0.01 - 0.1% w/w, and esbiothrin 0.01 - 0.5% w/w or imiprothrin 0.01-0.1% w/w and cypermethrin 0.1 - 0.3%.. 20 In another embodiment the composition preferably comprises three synthetic pyrethroids, most preferably wherein the synthetic pyrethroids are imiprothrin - 0.01 0.1% w/w, esbiothrin - 0.01 - 0.5% w/w, and d-phenothrin - 0.01 - 0.15% w/w. In a most preferred embodiment the aerosol composition comprises imiprothrin 0.02% w/w, esbiothrin 0.12% w/w and d-phenothrin 0.03% w/w. 25 Co-solvent - medium-chain-length (C 8

-C

2 ) alcohols The one or more Cs-C 12 alcohols is preferably aliphatic and preferably present in an amount of from about 0.02 - 20.0% w/w, more preferably about 0.1 - 10.0% w/w, more preferably about 0.5 - 5% w/w, more preferably about 0.8 - 2.0% w/w and most 30 preferably in an amount of about 1.0 - 1.5% w/w. Preferably the C 8

-C

1 2 alcohol is selected from the group consisting of octanol and isomers thereof (including 1-octanol, 2-octanol, 3-octanol), nonanol and isomers thereof (including 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol), decanol and isomers 35 thereof (including 1-decanol, 2-decanol, 3-decanol), undecanol and isomers thereof (including 1-undecanol, 2-undecanol, 3-undecanol, and 4-undecanol) and dodecanol WO 2006/111750 PCT/GB2006/001438 9 and isomers thereof (including 1-dodecanol, 2-dodecanol, 4-dodecanol, 5-dodecanol), or mixtures of the foregoing. In a preferred embodiment of the invention the C 8 - C 1 2 alcohol is selected from the 5 group comprising octanol, decanol and dodecanol, isomers thereof or mixtures thereof. Most preferably, the Cs - C 1 2 alcohol is decanol. Antibacterial actives (i) The antibacterial properties of quaternary ammonium compounds are widely 10 recognized. Quaternary ammonium salts generally comprise an organic nitrogen compound, in which the molecule structure includes a central nitrogen atom joined typically to four organic groups and a negatively charged acid radical. Octadecyldimethylbenzyl ammonium salt and hexamethonium salts are examples. Pentavalent nitrogen ring compounds such as lauryl pyridinium salt, are also 15 considered quaternary ammonium chlorides. Preferably the quaternary ammonium compound is selected from the group comprising alkyl-dimethylbenzylammonium saccharinate (Onyxide 3300TM, available from Stepan Company, USA), alkyldimethylbenzylammonium chloride, octadecyldimethylbenzyl 20 ammonium chloride, cetyl trimethyl ammonium bromide, myristalkonium chloride; and pentavalent nitrogen ring compounds such as lauryl pyridinium chloride. Most preferably the quaternary ammonium compound is alkyl dimethylbenzylammonium saccharinate (Onyxide 3300TM). 25 The one or more quaternary ammonium compounds are preferably present in an amount of from about 0.002 to 0.5% w/w, more preferably about 0.01 - 0.2% w/w and most preferably in an amount of about 0.1% w/w. 30 (ii) The C-C 4 alcohol is preferably present in an amount of from about 0.5 - 20.0% w/w, more preferably 1.5% w/w - 10% w/w, more preferably, about 2 - 7% w/w and most preferably about 3-5% w/w. Preferably the C-C 4 alcohol is selected from the group comprising ethanol, methanol, 35 propanol and isomers thereof such as for example isopropyl alcohol. Most preferably the C-C 4 alcohol is ethanol.

WO 2006/111750 PCT/GB2006/001438 10 Without being bound by theory, the present inventors believe that the C-C 4 alcohol contributes to the antibacterial properties of the compositions of the invention by increasing the "availability" of the quaternary ammonium compound. 5 Propellant One or more propellants are used in the composition of the invention in a total amount of from 3 to 90%. Amongst the propellants that may be used are hydrocarbons, fluorocarbons and compressed gas of which hydrocarbons and fluorocarbons are 10 preferred. In the case of the hydrocarbon propellants those that may be used include for example, acetylene, methane, ethane, ethylene, propane, propene, n-butane, nu-butene, isobutane, isobutene, pentane, pentene, isopentane and isopentene. Mixtures of these propellants 15 may also be used. Indeed, it should be noted that commercially available propellants typically contain a number of hydrocarbon gases. For example, an odorised commercial butane, available from Boral Gas contains predominantly n-butane and some iso-butane along with small amounts of propane, propene, pentane and butene. Preferred hydrocarbon propellants include propane, n-butane, isobutane, pentane and isopentane, 20 whilst most preferred are propane, iso-butane and n-butane. Particularly preferred hydrocarbon propellants are mixtures of propane, n-butane and iso-butane. Preferred fluorocarbon propellants are hydrofluorocarbons such as for example 1,1,1,2 tetrafluoroethane (HFC-134a), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227). 25 Whilst broadly the concentration of hydrocarbon or fluorocarbon propellant will be from 20 to 90%, generally the concentration will be from 50 to 90%, preferably 50 to 90% most preferably about 50 - 80%. 30 When compressed gases are used as a propellant generally these will be carbon dioxide, nitrogen or air. Usually, they will be used at a concentration of 2 to 10%, preferably about 5%. The person skilled in the art will appreciate that the pressure in an aerosol package will 35 be determined by propellant or mixture of propellant. This pressure will have a determining effect on spray rates. Hence for any particular valve system, varying the WO 2006/111750 PCT/GB2006/001438 11 propellant or propellant mixture will allow for the selection of a desired spray rate. Likewise for a particular propellant or propellant mixture, it is possible to select a valve and actuator system to achieve a desired rate. 5 Additional ingredients Solvents Solvents are optionally included to assist in the maintenance of stability and to enable the incorporation of an oil phase soluble insecticide. A solvent is preferably incorporated in the compositions of the invention in an amount of from about 0.01 10 50% w/w. Preferably, the solvent will be an organic solvent, in an amount of about 0.01 - 50% w/w. In one embodiment the solvent will be an organic solvent in an amount of about 5 - 50% w/w, more preferably about 15 - 40% w/w, more preferably about 10%-30% w/w and most preferably about 13% w/w, 14% w/w, 15% w/w, 16% w/w, 20% w/w, 40% w/w or 42% w/w. 15 The organic solvent may be aliphatic or aromatic but the organic solvent is preferably an aliphatic hydrocarbon. N-paraffin (preferably C 10

-C

1 3 ) is a preferred solvent, as are iso-paraffinic solvents and blends of aliphatic organic solvents. Examples of these are as follows: liquid n-paraffins-NorparTM 12, NorparTM 13 and NorparTM 15 (available 20 from Exxon) liquid isoparaffins-IsoparTM G, IsoparTM H, IsoparTM L, IsoparTM M and IsoparTM V (available from Exxon). The composition of the invention preferably further comprises a solubiliser which may otherwise be referred to as an emulsifier. The solubiliser is preferably a surfactant 25 present in the composition in an amount of about 0.01-2% w/w. In one embodiment the emulsifier is in the amount of about 0.2%-1.7% w/w, more preferably about 0.2% 0.75% w/w. The surfactant may be a non-ionic, anionic or amphoteric surfactant or a blend thereof. The surfactant is preferably a nonionic surfactant such as for example polyglycerol oleate, or a blend. Other nonionic surfactants that can be used include for 30 example fatty acid, alcohol, amine, alkyl phenol, and dialkylphenol ethoxylates, propoxylates and ethoxylate/propoxylate combinations; mono-, di- and tri-sorbitan esters; mono- and d-glycerides; polyoxyethylene sorbitol esters; and blends. Terpenoid solvents such as d-limonene and pine oil (max 5% w/w); dipolar aprotic solvents such as dimethyl sulphoxide (max 5% w/w); mono and di-carboxylic acid esters such as 35 butyrolactone (cyclic), alkyl benzoates, isopropyl myristate and isopropyl adipate (all max 5% w/w); and blends thereof, are also useful.

WO 2006/111750 PCT/GB2006/001438 12 Antioxidant The composition further preferably includes an antioxidant in an amount ranging from 0.001 - 0.1% w/w, more preferably in an amount of 0.005% w/w. The antioxidant is 5 preferably butylated hydroxytoluene (BHT), or butylated hydroxyanisole. The formulation may contain other additional components. For example, it may contain a perfume or fragrance. In one preferred embodiment the fragrance comprises for a natural or synthetic oil or blend, preferably for example pine oil. In this regard it 10 should be noted that pine oil may also be included as a solubiliser. Pine oil is particularly useful as a solubiliser for imiprothrin. Table 1 provides a summary of the preferred ingredients and preferred alternate ingredients which are suitable for use in the present invention. 15 Preparation The compositions of the invention may be prepared for example by adding one or more insecticide actives into the hydrocarbon solvent together with the solubiliser, antioxidant and optionally a fragrance. The antibacterial actives are mixed into the 20 cosolvent after which this antibacterial premix is added with mixing to the insecticidal premix. The combined mixture can then be pressurised into an aerosol container with the propellant. In each formulation provided in the following examples all the active ingredients are 25 represented as having a theoretical concentration of 100%. In practice pyrethroids used are generally technical grade material, with nominal concentrations as follows: imiprothrin 50%, esbiothrin 93% and d-phenothrin 92%. OnyxideTM 3300 comes as a 33% solution. Accordingly, when preparing the composition the desired concentrations of the aforementioned materials are accounted for and proportionately more of each 30 active is added to the formula. The n-paraffin solvent level is reduced to counter the increase in actives and to keep the total formula composition at 100%. The change in level of paraffin solvent is however minimal.

WO 2006/111750 PCT/GB2006/001438 13 EXAMPLES Example 1 - Comparative formula A Basic all insect killer formula. 5 Components Formula/% by wt Imiprothrin 0.020 Esbiothrin 0.100 d-Phenothrin 0.030 Polyglycerol Oleate 0.200 BHT 0.005 N-Paraffin C1O-C13 19.645 Propellant H46 80.000 Total 100.000 Example 2 - Comparative formula B Basic all insect killer formula further comprising antibacterial agents - 3% ethanol and 0.1% Onyxide 3300TM 10 Components Formula % by wt Imiprothrin 0.020 Esbiothrin 0.100 d-Phenothrin 0.030 Polyglycerol Oleate 0.200 BHT 0.005 Ethanol 3.000 Onyxide 3300TM 0.100 N-Paraffin C 10

-C

1 3 16.545 Propellant H46 80.000 Total 100.000 WO 2006/111750 PCT/GB2006/001438 14 Example 3 - Formula (I) of the present invention Basic insect killer formula further comprising antibacterial agents - 3% ethanol and 0.1% Onyxide 3300TM and cosolvent/synergist dodecanol. Components Formula/% by wt hniprothrin 0.020 Esbiothrin 0.100 d-Phenothrin 0.030 Polyglycerol Oleate 0.200 BHT 0.005 Ethanol 3.000 Decanol 1.000 Onyxide 3300 TM 0.100 N-Paraffin C 10

-C

1 3 15.545 Propellant H46 80.000 Total 100.000 5 Method for testing: Insecticidal Efficacy The test was conducted in a 28m 3 chamber by spraying the test formula for 3 seconds around the chamber. Fifty (50) female Culex quinquefasciatus mosquitoes were released and the knockdown of the insects was observed over a 15 minute period. For 10 each formulation 4 replicates were tested along with 4 replicates of an untreated control to ensure that the efficacy effects seen in the treatment tests was in fact due to the treatments. All replicates were randomised and the chamber was thoroughly cleaned between tests. 15 Results: Insecticidal Efficacy The efficacy results for the insecticidal formulas (Examples A, B and C) are presented in Table 1 and Figure 1. Table 1 Formula KD50 KD90 Example 1: Comparative formula A 125 440 Example 2: Comparative formula B 215 570 Example 3: Formula of the invention 155 440 20 WO 2006/111750 PCT/GB2006/001438 15 KD50 and KD90 refer to the mean time (in seconds) that it takes for 50% and 90% of the insects (respectively) to get knocked down. Accordingly, the smaller the number and the shorter the bar, the better the product. The numbers in Table 2 were calculated manually from raw data. 5 The KD50 and KD90 data shows that by including the OnyxideTM and ethanol in the basic formula, the efficacy of the insecticide activity was depressed, i.e. both the KD50 and KD90 results for Example 2 are significantly higher then in Example 1. However by further including 1% decanol the insecticidal activity determined by measuring the 10 KD90 was brought back to the same level as the basic formula and the insecticidal activity determined by measuring the KD50 was brought back close to the same level of activity as the basic formula. The mortality of the insects was observed again after 24hr. It was 100% for all 15 formulations. Antibacterial Efficacy Example 4 - Formula (II) of the present invention 20 Components Formula % by Formula % by weight weight aerosol concentrate Imiprothrin 0.020 0.100 d-Phenothrin 0.030 0.150 Esbiothrin 0.100 0.500 Polyglycerol Oleate 0.200 1.000 BHT 0.005 0.025 Ethanol 5.000 25.000 Decanol 1.000 5.000 Onyxide 33001" 0.100 0.500 n-Paraffin C 10

-CI

3 13.545 67.725 Propellant H46 80.000 Total 100.000 100.00 WO 2006/111750 PCT/GB2006/001438 16 Example 5: Formula (III) of the present invention Components Formula % by Formula % by weight weight aerosol concentrate Imiprothrin 0.020 0.100 d-Phenothrin 0.030 0.150 Esbiothrin 0.100 0.500 Polyglycerol Oleate 0.200 1.000 BHT 0.005 0.025 Ethanol 5.000 25.00 Decanol 1.000 5.000 Onyxide 3300 Im 0.200 1.000 n-Paraffin CIO-C3 13.445 67.225 Propellant H46 80.000 Total 100.000 100.00 5 Antibacterial efficacy was demonstrated by testing Formulas (II) and (III) of Examples 4 and 5 using the European standard suspension test protocol, EN1276. It is important to note that the concentrate was tested using this protocol. That is the formulation without propellant. The reason for this is twofold. Firstly, an aerosol cannot be tested using this protocol. Secondly, although the concentration of ingredients is higher in the 10 concentrate then the aerosol formulation, in fact in use, the ingredients will be in a concentration which is substantially that of the concentrate rather then the aerosol formulation. This arises out of the fact that the propellant is highly volatile. It will therefore be substantially removed from the formulation to the atmosphere upon dispensing of the aerosol. 15 The log reduction results are recorded in tables 2 and 3 respectively against the standard specified organisms. From these results, it is evident that both Formulas (II) and (III) of Examples 4 and 5 exhibited substantial antibacterial properties against the test bacteria. 20 WO 2006/111750 PCT/GB2006/001438 17 Table 2 - Example 4 Results Organisms Control Count Test Count cfu/ml Log Reduction cfu/ml 2.11 x 10 8 <100 >6.32 Pseudomonas aeruginosa 2.11 x 10 8 <100 > 6.32 Staphylococcus aureus 1.83 x 108 <100 > 6.26 E. coli 4.50 x 108 <100 >6.65 Enterococcus hirae Table 3 -Example 5 Results Organisms Control Count Test Count cfu/ml Log Reduction cfu/ml 3.90 x 108 <100 >6.59 Pseudomonas aeruginosa 2.40 x 108 <100 >6.38 Staphylococcus aureus 2.30 x 108 <100 > 6.36 E. coli 5.30 x 108 <100 > 6.72 Enterococcus hirae 5 WO 2006/111750 PCT/GB2006/001438 18 Example 6 - Formula (IV) of the present invention 0.02% imi, 0.12% EBT, 0.03% d-phen, 0.1% onyxide 3300, 4% DAA, 1% decanol, 0.2% PGO, 1.5% PINE OIL Ty"e P~ RY % % Ptny Ajse % L A_ 10000 Actv Imiprothrin 100.0 0.0200 0.1000 51.3 0.1949 19.493 d-phenothrn 100.0 0.0300 0.1500 98.1 0.1529 15.291 Esblothrln 100.0 0.1200 0.6000 95.5 0.6283 62.827 Polyglycerol TTT) , rs Oleate Ester 0.2000 1.0000 1.0000 100.000 Onyxide 3300 100.0 0.1000 0.5600 33.6 1.4881 148.810 Denatured Absolute Alcohol 100AG/F4 100.0 4.0000 20.0000 100.0 20.0000 2000.000 Pine Oil 1.5000 7.5000 75000 750.000 Decanol 1.0000 5.0000 5.0000 500.000 BHT 0.0050 0,0250 0.0250 2.500 n-paraffin solvent C10 C13 13.0250 65.1250 64.0108 6401.080 H46 ropelf propellant' 800000 Total 50.00 I 0000 5 WO 2006/111750 PCT/GB2006/001438 19 Example 7 - Formula (V) of the present invention, and preparation thereof TOTAL CIK - with 0.75% Pine Oil Component Fermul NmIna Pr'oduct ConcntMra AtIve Conrtte Tepateney % % jiy Adiusd -% 200.00 Acdive Cypermethrin 100 0.200 0.400 68.9 0.581 11.611 Tech (100% Imiprothrin 100 0.070 0.140 51.0 0.275 5.490 Salub#se Pine Oil 0.750 1.500 1.500 30.000 solvent DAA Ethanol 5.000 10.000 10.000 200.000 oupling Decanol 1.000 2.000 2.000 40.000 antioxidant BHT 0.005 0.010' 0.0101 0.200' dua Sipernat22S 0.100 0.200200 4.000 (Silicone Dioxide precip) osidual Aerosil R972 0.010 0.020, 0.020 0.400 (Silicone Dioxide fumed) FIffer Norpar 12 42.765 85.530 84.818 1696.358 Propellant Blend Propellant 50.000 H46 Tota 1 0.0' 10000 100.00020.00 5 Total volume of filled can is 250g Concentrate fill: 125-129g H46 Propellant Fill: 125-129g 10 Premix 1: 1. Add in formula quantity of Pine Oil, Imiprothrin & cypermethrin. 2. Turn on stirrer and mix till actives are dissolved. 3. Add in about 50g n-par. Continue stirring for 5 minutes or until all the Iniprothrin is dispersed. 15 Premix 2: 1. To a clean premix tank, add in the formula quantity of Alcohol, then Decanol then onyxide. Mix thoroughly. 20 Final Mix: 1. Add contents of the premix 1 & 2 tank to the final mixing tank.

WO 2006/111750 PCT/GB2006/001438 20 2. Rinse the premix tank with N-Paraffin (approx 50g each beaker), transferring rinsings each time to the final tank 3. Add about 10OOg of N-Paraffin to the final mixing tank. 4. Add the formula quantity of BHT (11125). 5 5. In a separate beaker weigh out quantities of Sipernat 22S (19687) and Aerosil R972 (19688). Add in about 50g N-par to form a slurry 6. Add the slurry to the mixing tank, rinse each drum with the remaining N Paraffin (2 x 273.2g) and add to tank 7. Stir for a further 10 minutes. 10 8. Sample for testing. 15 It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and 20 not restrictive.

Claims (22)

1. A non-aqueous aerosol antibacterial insecticide composition comprising: a) one or more synthetic pyrethroids in a total amount of about 0.001 - 1% w/w, b) one or more C 8 -CI 2 alcohols or mixture thereof in a total amount of about 0.02 5 w/w - 20.0% w/w, c) one or more quaternary ammonium compounds in a total amount of about 0.002 - 0.5% w/w, d) one or more C 1 -C 4 alcohols in a total amount of about 0.5 - 20.0% w/w, e) one or more propellants in a total amount of about 3 - 90% w/w, 10 f) optionally one or more pyrethroid synergists; g) optionally one or more other insecticides; and h) optionally one or more solvents.

2. The aerosol insecticide composition according to claim 1, wherein the 15 composition is a single phase composition.

3. The aerosol insecticide composition according to claim 1 or claim 2, wherein the one or more synthetic pyrethroid is selected from the group comprising: imiprothrin, esbiothrin, d-phenothrin, tetramethrin, allethrin, prallethrin, transfluthrin, 20 metofluthrin, resmethrin, permethrin, cypermethrin, deltamethrin, bifenthrin, lambdacyhalothrin, cyphenothrin, and cyfluthrin, including mixtures and isomers thereof.

4. The aerosol insecticide composition according to any one of claims 1-3 25 comprising 2 or more synthetic pyrethroids.

5. The aerosol insecticide composition according to any one of claims 1-3 comprising 3 or more synthetic pyrethroids. 30

6. The aerosol composition according to any one of claims 1 to 5, wherein the one or more C 8 -C 12 alcohol is selected from the group consisting of octanol and isomers thereof (including 1-octanol, 2-octanol, 3-octanol), nonanol and isomers thereof (including 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol), decanol and isomers thereof (including 1-decanol, 2-decanol, 3-decanol), undecanol and isomers thereof (including 35 1-undecanol, 2-undecanol, 3-undecanol, and 4-undecanol) and dodecanol and isomers WO 2006/111750 PCT/GB2006/001438 22 thereof (including 1-dodecanol, 2-dodecanol, 4-dodecanol, 5-dodecanol), or mixtures of the foregoing.

7. The aerosol composition according to claim 6, wherein the one or more C8 - C 1 2 5 alcohol is decanol or an isomer thereof.

8. The aerosol composition according to any one of claims 1 to 7, wherein the quaternary ammonium compound is selected from the group comprising alkyl dimethylbenzylammonium saccharinate, octadecyldimethylbenzyl ammonium chloride, 10 cetyl trimethyl ammonium bromide, myristalkonium chloride; and lauryl pyridinium chloride or mixtures thereof.

9. The aerosol composition according to any one of claims 1 to 8, wherein the C 1 C 4 alcohol is selected from the group comprising ethanol, methanol, propanol, 15 including isomers and mixtures thereof.

10. The aerosol composition according to claim 9, wherein the C1 - C 4 alcohol is ethanol. 20

11. The aerosol composition according to any one of claims 1 to 10, wherein the propellent is one or more hydrocarbons or fluorocarbons or a mixture thereof.

12. The aerosol composition according to any one of claims 1 to 11, wherein the solvent is present in an amount of 0.01 - 50% w/w. 25

13. The aerosol composition according to any one of claims 1 to 12, wherein the solvent is an organic solvent.

14. The aerosol composition according to claim 13, wherein the solvent is a C 1 0 .. 3 30 N-paraffin.

15. The aerosol composition according to any one of claims 1 to 14, wherein the composition further comprises a solubiliser. 35

16. The aerosol composition according to claim 15, wherein the solubiliser is polyglycerol oleate, pine oil, or mixtures thereof. WO 2006/111750 PCT/GB2006/001438 23

17. The aerosol composition according to claim 1, wherein the composition further comprises an antioxidant in an amount of 0.001 - 0.1% w/w. 5

18. The aerosol composition according to claim 1, including piperonyl butoxide as a pyrethroid synergist.

19. The aerosol according to any one of claims 1 to 18, wherein the other insecticide is selected from pyrethrum, dichlorvos, propoxur or mixtures thereof. 10

20. A method of killing insects comprising applying to said insects or to a target site of insect activity or infestation a non-aqueous aerosol antibacterial insecticide composition comprising: a) one or more synthetic pyrethroids in a total amount of about 0.00 1 - 1% w/w, 15 b) one or more Cs-CI 2 alcohols in a total amount of about 0.02 w/w - 20.0% w/w, c) one or more quaternary ammonium compounds in a total amount of about 0.002 - 0.5% w/w, d) one or more Ci-C 4 alcohols in a total amount of about 0.5 - 20.0% w/w, e) one or more propellants in a total amount of about 3-90% w/w, 20 f) optionally one or more pyrethroid synergists, g) optionally one or more other insecticides.; and h) optionally one or more solvent.

21. The method of killing insects according to claim 20, wherein the insecticide 25 composition comprises two or more synthetic pyrethroids.

22. The method of killing insects according to claim 20, wherein the insecticide composition comprises three of more synthetic pyrethroids.