Emulsion Concentrates of Lipophilic Compounds

The present invention relates to new, solvent-based emulsifiable concentrates of agrochemical active compounds, a process for the preparation of these formulations and their use for the application of the active compounds contained. Some terpenoid substances originating from plant extracts are known to be biologically active. For instance, the terpenes alpha-terpinene, d-limonene, para-cymene, have been shown to possess insecticidal and miticidal activity (WO-A 2010/144919), which could turn these molecules into useful plant protection products. This would be desirable since their biological activity is quite selective against the target pests. Moreover, alpha-terpinene, d-limonene and para-cymene possess a relatively benign (eco)toxicological profile.

At the same time, many of these terpenoid substances show a very limited water solubility, so that their use as plant protection products is challenging, because typical agricultural delivery systems are based upon using water as a vehicle carrier. Therefore, the use of such lipophilic terpenes as plant protection products is only possible when homogenous aqueous spray solutions of lipophilic terpenes can be obtained.

It was an object of the present invention to provide new solvent-based formulations based on lipophilic active ingredients, especially terpenes, which could form upon dilution with water a homogenous aqueous mixture. A homogenous distribution of the formulated lipophilic active ingredients (AI), especially terpenes, ensures that no concentration gradients of AI occur during the spraying of the spray solution. Otherwise the AI would not be able to induce a homogeneous and reliable biological performance along the application field. Additionally, a potential blockage of application equipment as a result of separated formulation particles/oil would be avoided.

It is also desirable that the process of generating a homogenous spray solution by way of mixing the formulated lipophilic AIs, especially terpenes, with water should succeed with minimum mechanical input.

Moreover, the resulting spray solutions should be physically stable for an amount of time relevant for the typical application conditions of formulated plant protection products on the field.

Therefore it was also an object of the present invention to provide stable formulations and that the lipophilic AI's, especially terpenes, and the aqueous medium should remain homogeneously mixed for at least 1 hour, preferably for a period of at least 24 hours.

A typical agricultural formulation for the delivery of lipophilic substances is an emulsion concentrate (EC). These formulations are based on non-water soluble solvents/components, which upon addition to water spontaneously generate an emulsion of the non- water soluble components in the aqueous medium.

An example is known whereby the preparation of EC formulations of lipophilic substances in butyl lactate is described (US-A 2007/0178128). However, these formulations fail to attain sufficiently long- lived homogenous spray solutions, so that substantial separation of the oil and water components is observed after 1 hour, and this separation is not reversible.

The present invention now provides a solution for using potentially biologically active lipophilic AI's, especially terpenoids, as plant protection products in the form of an emulsifiable concentrate. A method for preparing self-emulsifying novel emulsion concentrate formulations of lipophilic terpenoid substances is described. Additionally, the emulsion concentrate formulations according to the invention produce spray solutions which either remain homogenous for at least 24 hours, or which can be homogenized with gentle stirring and shaking when partially separating after 24 hours.

The aforementioned objectives were solved by providing a new emulsion concentrate containing one or more terpenes or mixture of terpenes, at least one lactic acid ester and at least one non-ionic surfactant, especially an ethoxylated fatty oil. The present invention is directed to pesticidal composition comprising a) one or more terpenes or mixtures thereof, b) at least one lactic acid ester, c) at least one water-immiscible solvent and d) at least one non-ionic surfactant. The present invention is also directed to pesticidal composition comprising al) one or more lipophilic insecticidal, fungicidal or herbicidal compound or mixtures thereof, b) at least one lactic acid ester, c) at least one water-immiscible solvent and d) at least one non-ionic surfactant. Preferred compositions according to the invention additionally comprise e) at least one anionic surfactant.

The compositions according to the invention are preferably emulsion concentrates (EC). As used herein, the term "terpene" or "terpenoid substance" refers to chemical substances of plant origin, containing between 10 and 15 carbons, and whose biosynthetic pathway may be attributed to the modification of Geranylpyrophosphate or Farnesylpyrophosphate.

When terpenes are modified chemically, such as by oxidation or rearrangement of the carbon skeleton, the resulting compounds are generally referred to as terpenoids. In the following the term "terpene" is used for terpenes ans terpenoids.

Terpenes are chemical compounds that are widespread in nature, mainly in plants as constituents of essential oils. Their building block is the hydrocarbon isoprene Examples of useful terpenes a) include citral, pinene, nerol, β-ionone, geraniol, carvacrol, eugenol, carvone, citonellal, terpeniol, anethole, camphor, menthol, limonene, nerolidol, farnesol, phytol, carotene (vitamin Al), squalene, thymol, tocotrienol, perillyl alcohol, borneol, myrcene, simene, carene, terpenene, and linalool.

Preferred terpenes a) are (rac)-camphor, p-cymene, (-)a-pinene, (rac)-citronellal, eugenol, geraniol, D- limonene, linalool, a-terpinene, and thymol. More preferred are p-cymene, D-limonene, a-terpinene

Preferred terpene mixtures a) are α-terpinene plus D-limonene plus p-cymene (6: 1.8:2.2), a-pinene plus (rac)-citronellal plus eugenol (1 : 1 :1), geraniol plus linalool plus (rac)-camphor (1 : 1 :1), a-pinene plus thymol (1 : 1), citronellal plus linalool plus thymol (1 : 1 :1), thymol (1 : 1) and eugenol plus linalool (1 : 1). More preferred are α-terpinene plus D-limonene plus p-cymene (6: 1.8:2.2)

Examples for lipophilic insecticidal compounds are azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methidathion, methyl-parathion, paraoxon, parathion, phenthoate, phosalone, phosmet, phorate, phoxim, pirimiphos- methyl, profenofos, prothiofos, tetrachlorvinphos, terbufos, triazophos, alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran,carbosulfan, fenoxycarb, furathiocarb, methiocarb, pirimicarb, propoxur, thiodicarb, triazamate, allethrin, bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, gamma-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin,chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine, ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin, juvenoids: pyriproxyfen, methoprene, fenoxycarb, spirodiclofen, spiromesifen, spirotetramat,clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid,endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram, fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim,acequinocyl, hydramethylnon, chlorfenapyr, diafenthiuron, propargitecryomazinepiperonyl butoxideindoxacarb, metaflumizone, chlorantraniliprole, cyantraniliprole, flubendiamide, tetraniliprole, benclothiaz, bifenazate, flonicamid, pyridalyl, pymetrozine, cyenopyrafen, flupyrazofos, cyflumetofen, bistrifluron or pyrifluquinazon.

Preferred insecticidal compounds are: allethrin, bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, lambda-cyhalothrin, gamma-cyhalothrin, permethrin, pyrethrin I and II, tefluthrin, transfluthrin, spirodiclofen, spiromesifen, spirotetramat,clothianidin, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, ethiprole, fipronil, abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram chlorantraniliprole, cyantraniliprole, flubendiamide, tetraniliprole, flonicamid, pymetrozine, cyenopyrafen or cyflumetofen.

Examples for lipophilic fungicidal compounds al) are: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone, cyazofamid, amisulbrom, benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide; diflumetorim, binapacryl, dinobuton, dinocap, fluazinam; ferimzone, fentin-acetate, fentin chloride, fentin hydroxide ametoctradin, silthiofam, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, imazalil, pefurazoate, prochloraz, triflumizol, fenarimol, nuarimol, pyrifenox, triforinealdimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine, fenhexamid, benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, octhilinone, bupirimate, benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone ,cyprodinil, mepanipyrim, pyrimethanilfluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonilquinoxyfenedifenphos, iprobenfos, pyrazophos, isoprothiolanedicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazoledimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate, oxathiapiprolinanilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid,guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianonpyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calciumchinomethionat, cyflufenamid, cymoxanil, dazomet, diclomezine, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, tolprocarb, proquinazid, tebufloquin, tecloftalam, triazoxideabscisic acid, ancymidol, 6-benzylaminopurine, brassinolide, butralin, cyclanilide, dimethipin, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, mefluidide, N-6- benzyladenine, paclobutrazol, prohydrojasmon, thidiazuron, triapenthenol, 2,3,5-tri-iodobenzoic acid, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluorometh yl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluorometh yl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide, 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4 -yl)- l,3-thiazol-4-yl]-4,5-diydro-l,2-oxazol-5-yl}phenyl methanesulfonate, 2- {3-[2-(l - {[3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l ,3 hiazol-4-yl]-4,5-dihydro-l,2-oxazol-5- yl}-3-chlorophenylmethane-sulfonate, (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4- methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-l,5-d ioxonan-7-yl2-methylpropanoat Lyserphenvalpyr) and uniconazole.

Preferred fungicidal compounds are: bixafen, fenamidone, fenhexamid, fluopicolide, fluopyram, fluoxastrobin, iprovalicarb, isotianil, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, ametoctradin, amisulbrom, azoxystrobin, benthiavalicarb-isopropyl, benzovindiflupyr, boscalid, carbendazim, chlorothanonil, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, difenoconazole, ethaboxam, epoxiconazole, famoxadone, fluazinam, fluquinconazole, flusilazole, flutianil, fluxapyroxad, kresoxim-methyl, mancozeb, mandipropamid, metconazol, pyriofenone, folpet, metaminostrobin, oxathiapiprolin, penthiopyrad, picoxystrobin, probenazole, proquinazid, pyraclostrobin, sedaxane, spiroxamin, tebufloquin, tetraconazole, zoxamide, ziram, N-(5-chloro-2- isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l -methyl-lH-pyrazole-4-carboxamide, N- (5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl )-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4 -yl)-l,3-thiazol- 4-yl]-4,5-diydro-l,2-oxazol-5-yl}phenyl methanesulfonate, 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH- pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-di hydro-l,2-oxazol-5-yl}-3- chlorophenylmethane-sulfonate, (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4- methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-l,5-d ioxonan-7-yl2-methylpropanoat Lyserphenvalpyr).

Examples for lipophilic herbicidal compounds are acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;butroxydim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; bromoxynil, dichlobenil, ioxynil; imazamethabenz, imazamox, imazapic, imazaquin;clomeprop, 2,4- dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop; chloridazon, flufenpyr- ethyl, fluthiacet, norflurazon, pyridate; aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; amidosulfuron, azimsulfuron, bensulfuron, chlorimuron- ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron; ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron; cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam; amicarbazone, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon- ethyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, diflufenzopyr, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyrafluf en- ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone.

When the terms lactic acid esters b) are used throughout the description, it is meant to include both optical isomers as well as mixtures thereof.

Suitable lactic acid esters b) according to the invention are lactic acid esters of Ci to Cn, preferred C2 to Cs, more preferred C2 to C4 saturated and unsaturated alkyl, C5 to C12 saturated and unsaturated cyclically Ci to C12 saturated and unsaturated branched alkyl lactic esters and mixtures thereof.

Preferred lactic acid esters b) are methyl lactate, ethyl lactate, n-propyl lactate, butyl lactate, 2-ethyl hexyl lactate, cyclohexyl lactate, 2-methylcyclohexyl lactate, heptyl lactate , octyl lactate, lauryl lactate, as either pure R or S enantiomer, as a racemate, or as an enantioenriched mixture.

A more particularly preferable lactic acid ester b) is butyl lactate which is an ester of n-butanol with lactic acid, preferably L-(+)-lactic acid, such as is obtainable, for example, as Purasolv ^® BL from Purac Bioquimica (Gran Vial 19-25, 08160 Montmelo-Barcelona, Spain) or Purac Biochem (Gorinchem, NL), or as Galaster ^® BL 97 from Galactic (Place d'Escanaffles 237760 Escanaffles - Belgium), or as Steposol ^® BL from Stepan (22 West Frontage Rd. Northfield, IL 60093-USA). Water-immiscible fluids c) are vegetable or mineral oils or esters of vegetable or mineral oils.

Suitable vegetable oils are all oils which can customarily be employed in agrochemical agents and can be obtained from plants. By way of example, sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, corn oil, cottonseed oil and soya bean oil, peanut oil, palm oil, coconut oil, linseed oil, thistle oil, walnut oil may be mentioned. Possible esters are ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, iso-propyl myristate, iso-propyl palmitate, methyl oleate, methyl palmitate, ethyl oleate, by way of example. Rape seed oil methyl ester and ethylhexyl palmitate are preferred. Possible mineral oils are Exxsol ^® D100 and white oils.

Suitable non-ionic surfactants d) are ethoxylated fatty oils. As used herein, the term "ethoxylated fatty oil" refers to substances which are classified under the CAS numbers 70377-91-2 (Vegetable oils, ethoxylated). Preferred are substances which are classified under the CAS numbers 61791-23-9 (Soybean oil, ethoxylated), 165658-60-6 (rape oil, ethoxylated) or 61791-12-6 (Castor oil, ethoxylated). More preferred non-ionic surfactants are CAS No. 61791-23-9 (Soybean oil, ethoxylated) and CAS No. 61791-12-6 (Castor oil, ethoxylated), most preferred is CAS No. 61791-12-6 (Castor oil, ethoxylated).

The ethoxylated fatty oil d) comprises 5 to 40 ethylene oxide units per molecule, preferably 10 to 30 ethylene oxide units, more preferably 10 to 20 ethylene oxide units.

In a preferred embodiment compound d) is ethoxylated castor oil which comprises 5 to 40 ethylene oxide units per molecule, preferably 10 to 30 ethylene oxide units, more preferably 10 to 20 ethylene oxide units.

Examples of "ethoxylated fatty oils"are given in Table 1. Table 1 : commercially available compounds d)

Tradename Company Average Chemical description

EO- Units

Agnique CSO 25 BASF 25 Ethoxylated Castor Oil

Agnique ^® CSO 30 BASF 30 Ethoxylated Castor Oil

Agnique ^® CSO 40 BASF 40 Ethoxylated Castor Oil Alkamuls ^® A Solvay 6 Ethoxylated Castor Oil

Alkamuls ^® 696 Solvay 13 Ethoxylated Castor Oil

Alkamuls ^® R/81 Solvay 18 Ethoxylated Castor Oil

Alkamuls ^® RC Solvay 22 Ethoxylated Castor Oil

Alkamuls ^® OR/36 Solvay 36 Ethoxylated Castor Oil

Alkamuls ^® OR/40 Solvay 40 Ethoxylated Castor Oil

Emulpon ^® CO-100 Akzo Nobel 10 Ethoxylated Castor Oil

Emulpon ^® CO-200 Akzo Nobel 20 Ethoxylated Castor Oil

Emulpon ^® CO-360 Akzo Nobel 40 Ethoxylated Castor Oil

Emulsogen ^® EL 300 Clariant 30 Ethoxylated Castor Oil

Emulsogen ^® EL 360 Clariant 36 Ethoxylated Castor Oil

Emulsogen ^® EL 400 Clariant 40 Ethoxylated Castor Oil

Emulsogen ^® EL 540 Clariant 54 Ethoxylated Castor Oil

Etocas ^® 5 Croda 5 Ethoxylated Castor Oil

Etocas ^® 10 Croda 10 Ethoxylated Castor Oil

Etocas ^® 15 Croda 15 Ethoxylated Castor Oil

Etocas ^® 30 Croda 30 Ethoxylated Castor Oil

Etocas ^® 40 Croda 40 Ethoxylated Castor Oil

Lucramul ^® CO 08 Levaco 8 Ethoxylated Castor Oil

Lucramul ^® CO 11 Levaco 11 Ethoxylated Castor Oil

Lucramul ^® CO 30 Levaco 30 Ethoxylated Castor Oil

Lucramul ^® CO 40 Levaco 40 Ethoxylated Castor Oil Toximul ^® 8243 Stepan 20 Ethoxylated Castor Oil

Toximul ^® 8241 Stepan 30 Ethoxylated Castor Oil

Toximul 8242 Stepan 40 Ethoxylated Castor Oil

Termul ^® 3535 Huntsman 30 Ethoxylated Castor Oil

Termul ^® 3541 Huntsman 40 Ethoxylated Castor Oil

Crovol ^® CR70 Croda 20 Ethoxylated Rapeseed Oil

Lucramul ^® S021 Levaco 21 Ethoxylated Soybean oil

Suitable anionic surfactants e) are mono- or diesterified phosphoric acids, which may be a compound of the general formula (I),

R3

I

R4

(I)

wherein

R3 is a hydroxy group or -(OCH2) _n OR5, R4 is a hydroxy group or -(OCH2) _m OR6, n is 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, m is 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, R5 and R6 are each independently of one another a hydrocarbon group, unsubstituted or substituted, branched or linear, cyclic, non-cyclic or heterocyclic, saturated or unsaturated, aromatic, non-aromatic or heteroaromatic comprising 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms, with the proviso that both R3 and R4 are not hydroxy groups simultaneously.

In a preferred embodiment of the present invention, the mono- or diesterified phosphoric acid may be selected from the group consisting of mono- and di-[octyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[octyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[decyl polyglycolether (4 EO)] phosphate as well as mixtures thereof, mono- and di-[decyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[decyl polyglycolether (6 EO)] phosphate as well as mixtures thereof, mono- and di-[decyl polyglycolether (9 EO)] phosphate as well as mixtures thereof, mono- and di-[undecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[undecyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[undecyl polyglycolether (6 EO)] phosphate as well as mixtures thereof, mono- and di-[undecyl polyglycolether (10 EO)] phosphate as well as mixtures thereof, mono- and di-[dodecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[dodecyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[dodecyl polyglycolether (6 EO)] phosphate as well as mixtures thereof, mono- and di-[dodecyl polyglycolether (10 EO)] phosphate as well as mixtures thereof, mono- and di-[tridecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[tridecyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[tridecyl polyglycolether (6 EO)] phosphate as well as mixtures thereof, mono- and di-[tridecyl polyglycolether (9 EO)] phosphate as well as mixtures thereof, mono- and di-[tridecyl polyglycolether (10 EO)] phosphate as well as mixtures thereof, mono- and di-[tridecyl polyglycolether (20 EO)] phosphate as well as mixtures thereof, mono- and di-[isotridecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[isotridecyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[isotridecyl polyglycolether (6 EO)] phosphate as well as mixtures thereof, mono- and di-[isotridecyl polyglycolether (9 EO)] phosphate as well as mixtures thereof, mono- and di- [isotridecyl polyglycolether (10 EO)] phosphate as well as mixtures thereof, mono- and di-[isotridecyl polyglycolether (20 EO)] phosphate as well as mixtures thereof, mono- and di-[tetradecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[tetradecyl polyglycolether (6 EO)] phosphate as well as mixtures thereof, mono- and di-[tetradecyl polyglycolether (10 EO)] phosphate as well as mixtures thereof, mono- and di-[pentadecyl polyglycolether (2 EO)] phosphate as well as mixtures thereof, mono- and di-[pentadecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[hexadecyl polyglycolether (2 EO)] phosphate as well as mixtures thereof, mono- and di-[hexadecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[heptadecyl polyglycolether (2 EO)] phosphate as well as mixtures thereof, mono- and di- [heptadecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[octadecyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[octadecyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[octadecyl polyglycolether (7 EO)] phosphate as well as mixtures thereof, mono- and di-[octadecyl polyglycolether (10 EO)] phosphate as well as mixtures thereof, mono- and di-[oleyl polyglycolether (3 EO)] phosphate as well as mixtures thereof, mono- and di-[oleyl polyglycolether (5 EO)] phosphate as well as mixtures thereof, mono- and di-[oleyl polyglycolether (7 EO)] phosphate as well as mixtures thereof, mono- and di-[oleyl polyglycolether (10 EO)] phosphate as well as mixtures thereof. Examples of "mono- or diesterified phosphoric acids" are given in Table 2. Table 2: commercially available phosphate ester surfactants (compounds e)

Tradename Company R5 and/or R6 n /m

(Average)

Phospholan ^® PS 541 Akzo Nobel CIO 9

Phospholan ^® PS 236 Akzo Nobel ClO-12 5

Phospholan ^® PS 222 Akzo Nobel C12-15 3

Phospholan ^® PS 131 Akzo Nobel C13 6

Atlox ^® AL-3382 Croda C8 5

Crodafos ^® D4A Croda CIO 4

Crodafos ^® T5A Croda C13 5

Crodafos ^® T6A Croda C13 6

Crodafos ^® Tl OA Croda C13 10

Crodafos ^® CS2A Croda C15-17 2

Crodafos ^® 03A Croda C18 3

Crodafos ^® 05A Croda C18 5

Crodafos ^® 01 OA Croda C18 10

Servoxyl ^® VPT 3/85 Elementis C8 3

Servoxyl ^® VPDZ 3/100 Elementis C13 3

Servoxyl ^® VPDZ 6/100 Elementis C13 6

Servoxyl ^® VPDZ 9/100 Elementis C13 9

Servoxyl ^® VPDZ Elementis C13 20

20/100 Servoxyl ^® VPFZ 7/100 Elementis C18 7

Empiphos ^® A5 D Huntsman C10-C12 5

Empiphos ^® 03 D Huntsman C18 3

Rhodafac ^® MB Solvay C13 3

Rhodafac ^® RS410 Solvay C11-C14 3

Rhodafac ^® RS710 Solvay C11-C14 10

Rhodafac ^® PA23 Solvay C10-C14 6

Rhodafac ^® PA33 Solvay C16-C18 3

Stepfac ^® 8180 Stepan C13 3

Stepfac ^® 8181 Stepan C13 6

In one embodiment formulations according to the invention contain compound a) in the concentration range of 1 to 45% w/w, preferably in the concentration range of 4 to 40% w/w, more preferably in the concentration range 9 to 30% w/w. In one embodiment formulations according to the invention contain compound b) compound b) in the concentration range of 10 to 65% w/w, preferably in the concentration range of 10 to 40% w/w, more preferably in the concentration range 20 to 40% w/w.

In one embodiment formulations according to the invention contain compound c) in the concentration range of 5 to 40% w/w, preferably in the concentration range of 10 to 40% w/w, more preferably in the concentration range 20 to 40% w/w.

In one embodiment formulations according to the invention contain compound d) in the concentration range of 3 to 30% w/w, preferably in the concentration range of 7 to 20% w/w, more preferably in the concentration range 10 to 20% w/w.

In one embodiment formulations according to the invention contain component e) in the concentration range of 2 to 20% w/w, preferably in the concentration range 3 to 18% w/w, more preferably in the concentration range of 5 to 15% w/w,.

Preferred pesticidal compositions according to the invention comprise a) 1 to 45% w/w of one or more terpenes or mixtures thereof, b) 10 to 65% w/w of at least one lactic acid ester, c) 5 to 40%) w/w of at least one water-immiscible solvent, d) 3 to 30%) w/w of at least one non-ionic surfactant and e) 2 to 20%) w/w of at least one anionic surfactant.

More preferred compositions according to the invention comprise a) 4 to 40%) w/w of one or more terpenes or mixtures thereof, b) 10 to 40%) w/w of at least one lactic acid ester, c) 10 to 40%o w/w of at least one water-immiscible solvent, d) 7 to 20%) w/w of at least one non-ionic surfactant and e) preferably 3 to 18 w/w of at least one anionic surfactant. Most preferred compositions according to the invention comprise a) 9 to 30%o w/w of one or more terpenes or mixtures thereof, b) 20 to 40%) w/w of at least one lactic acid ester, c) 20 to 40%o w/w of at least one water-immiscible solvent, d) 10 to 20%) w/w of at least one non-ionic surfactant and e) 5 to 15% w/w of at least one anionic surfactant.

The herein described emulsifiable concentrates may be prepared by sequential mixing of all components until a homogeneous liquid is obtained. The order of addition is inconsequential, and the mixing may be performed at any temperature, as long as the components are fluid. An example of a process is as follows: The terpenes (compound a) are charged into a suitable reaction vessel (e.g. glass flask, or stainless steel reactor equiped with stirring equipment). The remaining components b), c), d) and e) are added to the reaction vessel, and the mixture is agitated at room temperature, or above room temperature, until a homogeneous mixture has been obtained.

In one embodiment the pesticidal composition according to the invention is applied to a target area or host in order to control sucking, rasping and chewing pests, such as aphids, mites, white flies and thrips. In a particular embodiment the pesticidal composition according to the invention is applied to an insect, target area or host to control Asian citrus psyllids, green peach aphid, rosy apple aphid, spirea aphid, yellow aphid, black pecan aphid, turnip aphid, potato aphids, spirea aphid, silverleaf whitefly, sweetpotato whitefly, greenhouse whitefly, western flower thrips, eastern flower thrips, Florida flower thrips, onion thrips, chili thrips, citrus thrips, melon thrips, grape leafhoppers, variegated leafhoppers, and/or leafrniners (Liriomyza spp.). In another embodiment, the pesticidal composition according to the invention is applied to an insect, a target area or host in order to control Lepidopterans (adults and/or larvae), such as melonworm, codling moth, oriental fruit moth, spotted tentiform leafminer, redbanded leafroller, and/or green fruitworm. In yet another embodiment the pesticidal composition according to the invention is applied to a target area or host to control mites such as the two-spotted spider mite, the Pacific spider mite, the European red mite, citrus rust mite, citrus red mite, Willamette spider mite, and/or the strawberry spider mite. In another embodiment, the pesticidal composition according to the invention is applied to a target area or host to control insects or mites that vector viral pathogens, or bacterial or fungal pathogens, which insects or mites and pathogens are described in detail above, and include, for example, whiteflies and psyllids that vector, for example, squash vein yellowing virus (which causes watermelon vine decline) or organisms that cause citrus greening or zebra chip disease, especially in potatoes, respectively.

All plants and plant parts can be treated in accordance with the invention. Here, plants are to be understood to mean all plants and plant parts such as wanted and unwanted wild plants or crop plants (including naturally occurring crop plants), for example cereals (wheat, rice, triticale, barley, rye, oats), maize, soya bean, potato, sugar beet, sugar cane, tomatoes, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits apples, pears, citrus fruits and grapevines). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by varietal property rights. Plants should be understood to mean all developmental stages, such as seeds, seedlings, young (immature) plants up to mature plants. Plant parts should be understood to mean all parts and organs of the plants above and below ground, such as shoot, leaf, flower and root, examples given being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also tubers, roots and rhizomes. Parts of plants also include harvested plants or harvested plant parts and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.

Treatment according to the invention of the plants and plant parts with the pesticidal compositions according to the invention is carried out directly or by allowing the compounds to act on the surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above. The invention is used with particular preference to treat plants of the respective commercially customary cultivars or those that are in use. Plant cultivars are to be understood as meaning plants having new properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.

The treatment of the plants and plant parts with the pesticidal composition according to the invention is carried out directly or by action on their surroundings, habitat or storage space using customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, injecting, watering (drenching), drip irrigating and, in the case of propagation material, in particular in the case of seed, furthermore as a powder for dry seed treatment, a solution for liquid seed treatment, a water-soluble powder for slurry treatment, by incrusting, by coating with one or more coats, etc. It is furthermore possible to apply the pesticidal composition according to the invention by the ultra-low volume method or to inject the application form or the pesticidal composition according to the invention itself into the soil.

A preferred direct treatment of the plants is foliar application, i.e. the pesticidal composition according to the invention are applied to the foliage, where treatment frequency and the application rate should be adjusted according to the level of infestation with the pest in question.

In the case of systemically active compounds, the pesticidal composition according to the invention also access the plants via the root system. The plants are then treated by the action of the pesticidal composition according to the invention on the habitat of the plant. This may be done, for example, by drenching, or by mixing into the soil or the nutrient solution, i.e. the locus of the plant (e.g. soil or hydroponic systems) is impregnated with a liquid form of the pesticidal composition according to the invention, or by soil application, i.e. the pesticidal composition according to the invention are introduced in solid form (e.g. in the form of granules) into the locus of the plants. In the case of paddy rice crops, this can also be done by metering the pesticidal composition according to the invention in a solid application form (for example as granules) into a flooded paddy field.

The invention is illustrated by the following examples. Examples

In the preparation of the formulations in the following Examples the following components have been used:

The formulations were prepared by mixing the components as listed in Table 3 to 9. The stability of the formulations was measured by diluting the formulation example to 1% in CIPAC C Water at room temperature, in a 100 mL graduated cylinder, and monitoring the amount of cream or oil separated after lh and 24h. The results are given in Table 10.

Table 3: EC Formulations with single terpenes

Table 4: EC Formulations with Terpene Mixtures

Table 1: Terpene EC Formulations with different Lactic Acid Ester

Table 6: Terpene EC Formulations with different Vegetable oils

Table 7; Terpene EC Formulations with different Ethoxylated Fat/Oil

Table 8: Terpene EC Formulations with different Alcohol Ethoxylate Phosphate

Comparison Formulation according to US2007/0178128

Table 10: Emulsion Stability of Terpenoid Emulsifiable Concentrates

Emulsion Stability

Emulsion Particle Size

Formulation Example (mL of separated oil or cream)*

(d90, μπι)

1 h 24 h

1-1 0 0 28

1-2 0 0 27

1-3 0 0.25 20

1-4 0 0 19

1-5 0 0 7

1-6 0 0 8

1-7 0 0 22

1-8 0 0 5

1-9 0 0 2

1-10 0 0 1

1-11 0 0.1 4

1-12 0 0 9

1-13 0 0 14

1-14 0 0 1

1-15 0 0 12

1-16 0 0 8

1-17 0 0 17 -2 0 0 6-3 0 0 1-4 0 0 24-5 0 0 13-6 0 0 1-7 0 0 34-8 0 0 2-9 0 0 7-10 0 0 2-11 0 0.1 71-12 0 0.75 47-1 0 0.3 18-2 0 0.2 5-3 0 0.5 20-4 0 0.05 21-5 0.1 1.2 30-6 0 0 11-7 0 1 30-8 0.1 1 44-9 0 0.5 260-10 0 0.5 260-11 0 0.2 6 -12 0 0.3 6-13 0 0.1 12-14 0.1 0.3 7-15 0.1 0.2 23-16 0 0.1 5-17 0 0.2 3-18 0 0.05 5-19 0 0 14-20 0 0.5 80-21 0 0.05 110-22 0 0 27-1 0 0 11-2 0 0 7-3 0 0 17-4 0 0 20-5 0 0 22-6 0 0.5 20-7 0 0 0.5-1 0.1 1 78-2 0.1 1 1-3 0 0.5 12-4 0.1 1 40 -5 0 0.5 11-6 0 0.7 12-7 0 0 1-8 0 0.05 6-9 0 0.1 8-10 0 0.2 35-11 0 0 1-12 0 1 27-13 0 0.1 10-14 0 0.1 4-15 0 0 6-1 0 0 3-2 0 0.1 27-3 0 0 4-4 0 0 1-5 0 0 18-6 0 0.5 32-7 0 0.3 31-8 0 0.7 46-9 0 0.5 33-10 0 0.2 10-11 0 0.3 15 6-12 0 0.2 22

6-13 0 0 33

6-14 0 0 14

6-15 0 0.5 47

6-16 0 0 15

6-17 0 0 1

6-18 0 1 52

7-1

1 __t

(Example according to

US2007/0178128)

* Emulsion stability was measured by diluting the formulation example to 1% in CIPAC C Water at room temperature, in a 100 mL graduated cylinder, and monitoring the amount of cream or oil separated after lh and 24h. ^† Not measured due to the low stability of the emulsion after lh. ⁱ Not possible due to low stability of emulsion.