Title of Invention


Abstract ABSTRACT "OIL-IN-WATER FORMULATION OF AVERMECTINS" Oil-in-water emulsion formulations (EW) of avennectins based on esters of fatty acids as solvent and the use of such fonnuiations for the control of crop pests.
Full Text

Oil-in-waler formulations significantly reduces the amount of solvent used, but as disclosed by Mosin er at (Russian Journal of Ecology. Vol. 29. No. 1 1998. pp 127-129) Averssctin C for example tends to degrade significantly o\er time in the pre:ience of water and e^■en a faster degradation is observed if exposed to 5 light as disclosed b> Wislocki et a! in Ivemiectin and Abamectin. Cambell. W.C: Ed., Nevv- York: Springer-Verlag, 1989. especially pp. 184-185.
In European patent publication no. EP 1210877-Al and PCX publication no. WO 02/4348S-A1 it is suggested to formulate various insecticides, in particular D pyrethroids. as oil-in-water emulsions using one or more solvents from die group of esters of aliphatic monocai"box>lic acids, esters of aliphatic dicarboxylic acids, esters of ai-omatic monocai-boxylic acids, esters of aromatic dicaTbox>'lic acids and tri-n-alkylphosphates. and optionally a polai' co-solvent, SMC"; ;. ;V :jTiions are s::id t: '.c /.:':\t. :".:'.■ n :eichi::g as to the i:abi::\> c: ^^e
PCT publication no. WO 2004/0938S6-A1 discloses topical reaa;--to-use pharmaceurlca"; compcsitions comprising !\-ermectin for human treatment of ibe sldn disease rji:acca. The compositions cC'raprise an oily phase compnsing one
0 or moi"c fat:> >\:bs!ance!i. surfactant, ?ol\'enl- gelling agents and w^ater. Tiie fart;.' substances a;-^ ■\g. selec'.cd among syrthe[i.': oil?, preferably .in combination vviih a silicone oiJ. "I'nc compositions comprise a icw proportion ot ViSter mimissiplc co-sol'.cnr to i\-ei"n-iectin and are nut suitable ;'or agrochemical use. i.e. in diiuL:ri form fi.-;" crop protection, as the;-' are o: a hish \"iscosit;' and the amount o; 'A'ater
;5 irnmiscioic consdt',;en:s. i.e. f:aiy ^ubslanc-t';. arc insiifficienl to keep ine dci!'C ingredient dissolved especially after dilution with eg. vv'ater,
PCT publication no. WO 95.'3LS9S-AI discloses fomiu'ations of various insecticides, in particular pyrethroids. as oi!-in-water emulsions using one or
;0 more so:\"ents from the group of esters of phthalates or fatty esters derived from vegetable oils, and optionally a polar co-solvent. Howe\'er. it is no: suggested

that the compositions have a beneficial effect on the stability of the active ingTedient(s) itself.
In European patent application no. EP 933025--A1 emulsifiable concentrates of fungicides or herbicides are disclosed comprisins esters of plant oils and water-miscible polar aptotic co-soh'ents.
In United States patent no. US 5.227402 aqueous microemulsion formulations of Abamectin are disclosed (e.g. example 11), Although the formulations are said to be stable, no teaching as to the stability of the active ingredient itself is found in the specifications.
Further, microemulsions require use of large amounts of surfactants to ensure itabil:!;- of v:e :"-J-:"iod"cpIe:s in '.he aaiiecii^ 'r:hz, U'ansparent or semitransparent preparations with oi] droplets usuall; of a magnitude of 10-200 nm. oihin-vvater emulsions are nor.-tiTinsparent and the oii droplets of a magnitude of 1-20 \im. Howe'-er using high pressure homogeniza'dcn techniques or similar means in the i;repaJ"ation process can p-ovide oil-iri-vv3ter formujations having a.n oi' dropiei ^ize heiov; 1 \ini.
In European paten: speciilcation no. EP 4.'>65.>A2. stable micro emulsions of h-enuectin suitable for psrental or oral adnrnist:ation arc provided usij:g co-solvents selected amiong glycerol formal. ^ropUene glycol, glycerine or polyetliylenc glycol. The micro emulsions can be fuitlier stabilised with inclusion of one or more substrates selecied among benzyl alcohol lidocaine, a paraben or choline.

significant siabilisaiion of the aveimectin compound itself can be pi'epared based on esters of fatty acids as organic solvent.
Description of the invention
The present invention relates in one aspect to a concentrated oil-in-v-'ater emulsion formulation for crop protection against pests, comprising
a) one or more pesticidal active ingredients selected among avermectins.
b) one or more solvents selected among esters of fatty acids.
c,l an emulsifier system comprising one or more surfactants,
d) water, and
e) one or more co-soh'ents having a solubility in water of less than 10% at 25 X.
wherein the pH-\'aliie of the err;uision is liigher than 3 and tl'.e amount by w^eight cf c^-?olvprit i> c3ual IG rr w.z-::-:' :h.:::": v:.z amount b^■ ■■■ eic." J: :^ v e;"rx-7nr.
the active ingredients compai'cd to oil-in-water formuiations comprising a'.'erm:ecrins according to the prior an and maintai:! the beriefirs of oii--n-water emulsions. Further. tJie formuIaiiGns significantly reduce the degraciadcn of the aveiTnectin(s) also wlien exposed ro lighl.
The prc.se;it invennon further pro\ide.? ?, method for 5:abi]ising a\"en--ectin? in oi'-:r,->vater emulsion fonnulanor;? -jsiiig rhe above com.positio]:, FretVrabiy fhc formiil.i'ions provide stabilisation of :he a\'ermectin(sl to an cxteni that Itss than about 59c. more preferably 3Sc. of die irjiiial concentration 01 the a-, ernK"-ctin(sj has degraded when the formulaticns are stored at 54'C for 14 day-;: or less than about 10^7c, miore preferably 5%. of the initial concentration of the a\-cnncct!n(s) ha? derradcd v/hen the 'onniiiadons are stored at 70°C for 14 day?.

The lerm oi]4n-water emulsion formulation means the undiluted formulation. For the purpose of this invention, all percentages expressed herein are percentage by weight, unless otherwdse specified.
The avermecun(s) is e.g. selected among Abamectin. Aversectin C. Doramectin. Emaraectin. Eprinomectin, Ivermectin, Selaroectin and salts thereof and especially selected among Abamectin, Aversectin C and Emamectin. mixtures thereof and salts thereof . e.g. Emamectin benzoate, with Abamectin being the most preferred choice.
The concenfation of die avermeclins(s) is generally between 0.001 and 30%.
preferably 0.1 and 10%. and more preferably ] and 5% b}' weight of the total composition (9rwAvj.
obtainabl; from medium chained fatty acids by esterification with aik.inols. and include iC-Cini-alkyI I'Cf.-CiiJ-fatty acid esters. Preferred fatty acids of these plant o:h- ':;t\c a carbon chain length of 5 to 20, in particular 6 to IS carbcn atoms. In a prefen.-ed embodiment the alky) part c - -he fatty acid esters CG!I >is; c\' J-18 c.;rbon ato.ms (straight or branched). Prcfenbly {Cj-Csj-alk} i --.:.'vx :-!» used le.2- n-jCth\i, ethyl, propvi. iso-propyL buiyl. iso-buly), sec-buiyi, p;-]rt_v i and hexyl). more prcfcrablv the alkyl part consist of 1--3 cai-bcn anj:y;i. e\;.!' more preferably 1-.- cai-bon atoms, and most preferably methyl cslcr.: of pbi.-^; oils a'£ used, and even more preferably itJClhylated plant oils whej-e^'-. tii:: fait-acid ha^ a carbon chain lengdi between 7-16, iTiOrc preferably 8-14. Hvr.inpic'. of esters of fatt}- acids are Stepan C-25 methyl ester, Stepan C-40 meth)! ester. Stepar, 553 or S:er;an IPM aH available from Stepan. or Wiicono: 2301, Witconol 2307. Witconol 2308. Witconol 2309 all available from. Witco Corporation, or ethyl caproate available from Sigma-Aldrich. or Edenor ME C6-ClO. Edenor VIE C12 9S/100 both available ^om Cognis or Tesosoft MM and

Tegosoft: SH both available from Goldschmidi. as well as the Agnique ME series of products available from Cognis such as Agnique ME 890-0 and Agnique ME 12C-F. It is advantageous to choose esters of fatty acids with low viscosity to ease formation of the oil-in-water formulation. Further, as the
solubility of The avermettins \'aries among the esters of fatty acids, one may advantageously choose among those having as high a solubility of the avermectin as possible without the need to apply e.g. heating to increase solubility of the avermectin or vigorous stirring during the preparation of the oil phase for the oil-in-water formulation. However as illustrated herein, esters of fatty acids either having a solid or waxy consistency at room temperature are also useful.

The amount of esters of fatty acids is generalh' betvi'een 5 to 50%, preferably
10-40% and mer4e preferbly 15-30% by weight of the total composition
Fatty acids are usualh- obtained from a natural source and are therefore mixtures of acids v^■ith various chain lengtl'iS. As used herein, the carbon number of a particular fatty scid refers TO the number of cai-bon aton-,3 of tlie main acid component, i.e. the conipcrient pre-\'ailing in the highest smcuni, Thu'--. apart from a;i ester of a fatf-' acid liaving a specified carbon number, nunor E;moi:n:s of esters of fatty acids ha\ ins a sir.alier or higher amount of carbon aioms in ino acid part mav occur. A:, an e.-xample methyl ccconatc usuallv comprises about 45-55% of the main C12 :-?-iethyl ester, the rest being methyl esters of ac:d> having 6, 8. 10. 14, ]6 or "IS carbon atoms in \?jious but indi\iuua;ly less amounts ■-han the acid ha\"ing 12 carbon atorns.
The emj.uisifier ^'.'srem : comprising one or more suifactant- is chosen among anionic, cationic. nonionic. zwitterionic and polymer surfactants or mixtures thereof.

Examples of suhable anionic surfactants include akali, alkaline eanh or ammoniiim salts of the fatty acids, such as potassium stearate. alkvl sulfates, alkyl ether sulfates, alky 1 sulfonates or iso-alkylsulfonates. aik}-Ibe::zene5uifona-tes sucii as sodium dodecylbenzenelsulfonale, alkybaphthalenesulfonates, alkyl methyl ester sulfonates, acyl gluiamates. alkylsulfosuccinates. sarccsinaies such as sodium lauro\'l sarcosinate. taurates or ethoxylated and phosphor>"lated styryl-substituted phenols. Examples of suitable cationic surfactants include halides or alkyitrimetliylammonium alkyl sulfates, alkyIpyridinium halides or diaIk>;dimethy1ammonium halides or dialkyldimethvLammonium alk\-l sulfates. Examples of suitable nonionic surfactants include alkoxylated animal or vegetable fats and oils such as com oil etiioxylates. castor oil elhox)'];-ies. taio fat eii-iOxylates. glycerol esters such as glycerol mcnoslearale. fatty alcohol £ikox>'lare3 and oxoalcoho! alko\yla:es. fatty acid alkcxyjates svich as oleic ?LC!d ?th::-;;"'.:.;i. ^'.^c^'lrnei^oi a.;C-:~ .I'.f. r./' :,; isc::-:^y^r ■i"":C'. :■;."-""-/::_ ^ :.'.cth^iellC sorbitan fatty acid esters. aik>"l polyglycosides. etlio"nylatec styry]-?!;'-stituted phenols, N-alkylgluconamidcs. aikylineth)! sulfoxides. aii-;\ ;di:"nc;hyl-i;hosphl:ie oxides such as tetradccyldiriethj'lphosphine oxide, i

i Hsarijles of rolymer surf;xta[".t:^ ^ucViCe di-. rri- cr ii"iUi=")-rlo.K ri'k V!:""- c. mc lABjv. ABA and BA3 t)pL-, ifiich i-^ polveth>]ene -.ly.'idi biock p;.';. p-^-;-';. .cn-r oxide, poiystyrene block ^l^l^■cth}le^e oxide. AB comn puAr^cr^ ^-ich :,s '">'!'■■~~'-'ha'~"''"e CJ^"'"" ~!~.lve'f ■> j'"'e r~""ide or r^ol'-'acr'.ia's cc"-ib ooA'^ihvlen; Gxice.
The sur^actanrs mentioned are akknov.T! compounds.

The amount of surfactanT(s) in the formulations is generally between 0.1-20%. preferably between 0.5-15^ and more preferably between 1-I09c b>- weight of
the total composinon %w/w
It i5 preferred to use as emuhifier system, solely one or more surfactants i selected among anionic surfactants, more preferably anionic surfactants selected among ethoxylated and phosphorviated styr\l-substimted phenols and alkvl ether sulfates.
To further improve the stability of the a^"ermectin(s) and the formulation as ) such, one or more co-soh"ents, i.e. component ei which a]'e different from tlie components bh are included in the fonnulaticns and said co-solvents are totally insoluble or only sparingly soluble in \^-?.ter. By sparingly soluble in water ii meant co-solvents that have a solubilitv in water of less than 10 g or 100 ru
.Arnold (1996) or The Properties of Sohxnts. Yizhak Marcus, pubiished D> Wilex" (199S). especially table 4,6. By incorporating a \vater insoiubie co-soivc;-; the soubihty of the avermation in the oil phase of the formulation is increase
! and secures that the avermectins remain before and .;fter dihuion a; the concentrated compositions to use concenrns. By remamuig after dikition crystallization of tlie actiw bigrcdient and in, turii b'cclfii ^ ef filiei-s and/or nozzles in the spray equipement during applicaiton avoided Ftirtbci". \o easure a high and last biological activit;, :1 is JLUportan; ;bat iba
' avenrectins are delivered to the target oest ir creop infested or l9ikely to be: The skin or plant material, as avermectins will degrade quickly vvhen tvpo.;ce direct'y to light on the treated surface, important targe: pests cf usuallv of the suckins and chewing type, thus the pest needs to ingest, i.e. by

che-vv'iiig or sucking on plant maierial for the avennectins to have the highest
Among examples of co-soiven:s are aromatic hydrocarbons derived from bee.-*-.., ;-ach £.s. for example, toiuene. xylenes, mesitylene. dusopropvlbenzene and its liigher homologs, indane and naphflialene derivatives, such as 1-methylnaphthale.ie, 2-methylnaphthalene: C5-C12 aliphatic hydrocai-bons (.straight, branched or cyclic), such as, for example, pentane. hexane. cyclohexane. octane, 2-ethyIhexane. decane: C5-C10 aliphatic alcohols (straiahi or branched), in panicular C6-C9. such as hexanoL 2-eThyl butaijol. heptanol. octanoh 2-octanoI. and 2-ethylhexanol: aromatic alcohols such as benzyl alcohol, cyclic aliphatic ketonei such as c>c!ohexanone: mixtures of ai'omatic and aliphatic hydrocarbons, s-jch as. for example, the coiTesponding "[iroiTiitic"
a:'oniatic hydrocai-bons. such as chlorobenzene, and dichlorobenzenes: and mi\ti^res thereof.
Am.ong prefeiTcd co-sol\'ents are straight, branched or cyc-jc L:'-Ci2 alii,ihatij hydroca:'bons; straight or branched C5-C10 alipliaiic rdcohi.j's; CjCi-,:- alirii?,:!!."' ketoue? and mineral oils as well as mixtures thereof. More }.reler;--;a i.vc sii-aii^ht or brar.ched C5-C10 aliphatic alcohols and cyclohexa:-oiie. of/Lior.-Jly i:; combination '■xith one or more mineral oils. Ii^cxanol '-i' :.'Cl;::\ol bei^ii: pariicuhu-h' preferred as the C5-C10 aliphatic alcohol and i\ r'p:i'j^r;.p. i;scJ '■.■-' combinatioii Aim one or more mineral oils.
The amount of co-soJvenr,s. is generally betv een 0.1-50'K pirffrabiy \-15'^-and more preferab'.v 5-20'A- fTf W/W).

To obtain the desired stability of avermectin in the oil-in-water emulsion, a certain amount of co-soivent having a solubility in water of less than IG'^c at 25'C is required. .According to the invention the amouni of co-soh-ent is at least equal to die amount of avermectin. Suitabl;-, the amount of co-solvent is higher than the amount of a^'eimectin by weight ;w/\^~i. In an aspect of the mvention. the v/eighl ratio of a\'ermectin to co-soh'ent is fi-om 1:1 to 1:100. preferably 1:1 to 1;50, and most preferred 1:1 to 1:20. Without it being desired to be bound by tl:eory. it is presently be!ie\'ed uiat die co-solvent helps maintain the a\-emtectin solubilized in the oily droplets of the emulsion. In the event, the am_ount of co-soi\-ent is lower than the amount of avermectin a tendency for the acti\-e component to precipitate is obseived, especially after dilution of the concenirated emulsion of the in\ention with waicv. However. "-A-iie:! tiie amount of eo'-soi«"ent is at least equal io the amount of avermectin. the acti\"e constirjent
. .■: : ":'r:^ 7:~iuJs^ons.
li ':'ii.'i been found that the pH \-3lue o: liie emulsions, i.e. prior tn diiutic:-. 'r t'or e::'-:.-rii]c spraying equipment, have an influence on the :>;aoi-iry of \V.c L'o ei-mcclin. if the pH-value of ihe final e.mulsion is lower than 3, .; 'Aiir^nccsil {iC-j- aJiUion or" the active ing-edieni is obseiTed. A prek-::':^.". /-i-i e' ;:': cj;i' Isio]".s p3"ior lo dilution is hetv^een 3 and 12. more prelerabS;. ' .!,]i"_ ] . ■,,■■::; \L: :::?VO pieferably 4 and 1 "1 and e\-en more proferabh' 5 and :■_■. ■.■ v;. :■ -'A ■;:" c-9 beu:^ Dotl prefeired, Howeser. ore need not necessaidl}' :■/.". _ '■;-a:'i;::-U:rs as the 0 'nuisifier system by itscill including anv optionally au\;ha;";v:\ .Icp^mLirg on ch^u.:e OT componenis. may ensure that the pH-\'alue of inc rna; ■.rT:\i'i■^■ i i> '.vithin tiie urefen'ed range. If appropriate, the amounts of pH-ad_;;:>^:crs' '^ .r'. '~-nes ODUon tu; are suitably present ic ensure a pK-^-alue of the emul:^:n :u£:hrr '.-.ZT. 3. Depending on solubility, the r-H-adjusters are included in either the organic jr aqueous phase. pH-adjusters include both acids and bases of the orga;v,c or

inorganic type. Preferred pH-adJusrers include organic acids and alkali metal compounds. The organic acids include those such as citric, malic, adipic. cinnamic. fumaric, maleic. succinic, and tartaric acid, and the mono-, di-, or tribasic salts of these acids are suitable organic acid salts. Suitable salts of these acids are ihe soluble or meltable salts and include those salts in which one or more acidic protons are replaced with a cation such as sodium, potassium, calcium, magnesium, and ammonium. Alkali metal compounds include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate. hydrogencai"bonates of alkali metals such as sodium hydi'Ogencai-bonate and alkali metal phosphates such as sodium phosphate.
Funher optionally auxiliaiies uhich m.ay be included in either the organic or ?iC::::: : "....^c .^^ c::^:::^ on i:.::ir':!::y i :"ch:Sc :h:ckeners, film-ferr::r..^
protectants and cue or more additional insecticides different from the avermectir/s'i. Such auxiliai-ies are generally known within the ait o:' agiT'chemJca! formulation chemistiy. and although a specific ingredient :i classified a? '""aJling within one category, it m.ay well sen'e the purpose of an> oi' the others.
Tiuckcners and film-forming agents include stajches, gums, casein a'ld gclati'ic. pol\">:nvl pyn-clidoncs- pol\"ethyleiie and polypropylene gKcols. poh^.c]-) ia",:^. polsTicrylamioe?, poj^ethyleneimines. poly\inyl alcohols. pol\\irjyl r.cer:^::-'.. and rnetlivl- - h\droxyith\l- and hydro-.yprcpytcelluloses and deri\';vi\-e^ tre^-,"'i.'f
Exaniples :^f the antifreezing agent include ethylene gh'col. dieth>-lenc glycol. ;3ro")"iene glycol and the like.

Typical preservatives include methyl and propyl parahydroxybenzoate. 2-brorao-2-nitro-propane-13-diol, sodium benzoate, formaldehyde, glutaralde-hyde. 0-phenylphenol, benzisothiazolinones. 5-chloro-2-methvl-4-isoiiiiazoliD-3-one. pentachlorophenol. 2-4-dichloroben2ylalcohol and sorbic acid and deri\"ati\'es thereof.
Preferred anti-foaming and defoamer agents are silicone based compounds e.g. polyaikylsiloxanes.
Tilt optional additional insecticide including acaricides and nematicides) can advantageously be included for example to w-iden the spectrum of action cr to prevent the biiiid-up of resistance. Suitable examples of such additicna! insecticides are e.g.: accphaie, acetamiprid. acrinattirin, alanvcarb. aldicarb. :::'L.hancLhr^r. ..:£iz::z. :";..• ^^dii'a^hnn. azinpix?. s.z"C\ c"::.i:i, Bru!!!:!>.
butocarboxin, biitylpyiidaben. cadusafos, carbarv'l. carbofuran. carbophenothion.
ci'irbnsv.lfan. cartap. chloethocai-b, chloroethox\'fos. chlorfenapyr.
chlornfe-ri\inphos. chlcrofluazuron. chloromephos, chiorpyrifoS:
c^jQipafenQziae. cis-resmethrin. clothianidin. ciocytluin, cJofentezine.
cvancplio?. cvcloprothi-in. cyiluthrin. cyhalothnn. cyhexa'.in. cypermeihrin.
cyromazi'jc. deitamethrin. demeton. difenthiuron, diaziROu. d:c'Ldij?e^tluon.
dich]or\ OS. dirliphos. dicrctophos. diethion. diflubcnzur-or,. ciimetlioaTC,
dimefnvlvinphos. dinotefurai;. oioxathion. disulfoton. edifer.phos. csfc:V'"a]eraTe. ■ cthiofencarb. ethion. cthofcnprox. ethoprophos, e;o.\a>.olc. euimphos.
feiicin-iphos. fen/aquin. fenbutatin oxide, fenitrothion. fcnobucarb. ivnoThiocarh.
fenoxycarb. fen prop athrin, fenpyrad. fenpyroximaie. fenihion. fcn\ aierate,
npronil. fior.icamid. f^uazinam, fluazuron. fluc>-cloxi;ron. tlucUhrinate.
fiUfenoxuron, flufenprox, fluvalinate. fonophos, formothion. fosthiazate. ) fubfenprox. farathiocarb, gamma-cyhalothrin. HCH. heptenophcs,
hexaflumuror;. hex^Thiazox. inaidacloprid. mdoxacarb. ■prober,.fcs. isazophos.

isofenphos. isoprocarb, isoxathion, lambda-cyhalothrin. lufenuron, malathion, mecarbam. me\'inphos. mesulfenphos, metaldehyde. methacrifos. methari!dopho5. methidathion. methiocarb. methomyl. methoxyfenozide. metolcai'b. milbemeclin, monocrotophos, moxidectin, naled. nitenpyram. omethoate. oxamyl. oxydemethon M. oxydeprofos. parathion A. parathijn M. ■:ermethrin. phenthoate, phorate, phosalone. phosmet phosphamidon, phoxim. pirimicarb, pirimiphos, profenofos, promecarb, propaphos, propoxur, protiiiofo?. prothoate, pymetrozin. pyrachlophos, pyridaphenthion, pyresmethrin. pyrethrum. pyridaben, pyrimidifen. pyriproxifen, quinalphos, salithion. sebufos, silafiuofen. spinetoram, spinosad. spirodiclofen, sulfotep. sulprofos, tebufenozid, tebufenpyrad, tebupiiimiphos, teflubenzuron, tcfluihrin. lemephos, lerbam, terbufos, letrach]o^^"jnphos. JhiacJoprid, ihiafenox. thiamelhoxzi~n thiodicarb. thiofanox. ibiomeihon. xhionazin. thuringiensin. tralomethiin. *.':z:'alhe:.. T::izcpho?- '::".? '-:■'■ 'r:c::..zrfGn. triflurriuron. '":n'--h?.y:.-]:b.
!f present it is preferred to include one or more insecticides chosen among the natural or synthetic pyrethroids e.g. as found above and especially chosen among acrinatlirin, cypermethrin. cyfliitkrin, cyhalothrin, deltametluin. fenvalerate a7~d tefluthrin. inclnding any of the previous mentioned compounds in its pii-tiall;' or fully rescls'ed isomeric form. Particularly prefcrrc-d is acrinathiin or ganima-C}'halothrin.
The s'jbstni:i;on of the additional insecticide and/or further addiiion of other known aotr\'s compounds, such as herbicides, fungicides, fertilisers or grnvvth regulators. :; also possible.
The invention also relates to a process for producing an oi'.-m-v.-ater em/ulsion formulation as described herein comprising the steps of:
I. preparing an organic phase comprising the one or mere esters of fam acids, the one or more avermectin(si. the one or more c^o-sol\'en:t^si

having a soiubiliry in water of Jess than IO-TT^ al 25°C. and opnonaliy further auxiliaries in tlie organic phase;
II. preparing an aqueous phase comprising water, the emulsifier system comprising one or more surfactants, and optionally further hydrophllic Euxiliaries: and
III. mixing the organic phase and the aqueous phase under agitation to obtain an oil-in-water emulsion.
As the skilled person will easily recognise, the order of addition of tlie \aiious ingredients used in both the orgaiTic and aqueous phase is of minor importance. This also applies to the order of combining the organic phase with the aqueous
phase. Some of the optionaliy auxiliaries ma; even be added after the nixing of the organic and aqueous phase. One sidhed in the art will further recognise tliat a!',\ one c: :i ':~r.c:'' cf ai:ra:"Vv^ n":a"' z; ^~z'^ 'c ::co!rr';sh the iVLixi:-;; j:e"Di.
intensi\'e liomogenisation is a conceivable method. In either of the above steps. heat may be applied to ease the formation of a homogeneous phase.
The invention further relates to the use of oihin-water emulsion foi7Tiulatio!is as described herein for the control of pests and protection of crops against such pests, said use comprise appiying tlie emuision, preferabl.v in diiUted fGira (e.g. aqueous dih.Ued fonrO- to the pests or to plants, plant seeds, soil, snrfaces and :';-,e like infested v\ifn pesis or likely lo be occupied by pesrs. Per crop protection purposes, the fomiuiations of the present invention can bo used to figiU pests .such as for exnir>vls aphids, Jiiites. ijcs, nematodes, acarina. rcacr.e.-;, ants and the like that infest or is likely to uifest crops.
The formulations according to the invention are particular suitable for use against ;>csts from the genera .-^culus. Alabama, .\nticarsia, Hemusia,

Chonstoneura, Epilachna, Frankliniella. Laspeyresia, Leptinotarsa, Liiiomyza, Lymantria. Keiferia. Panonchus, Phrorimaea, Phyllocnisti?. Phyllocoptruta. Pieris. Plmella. Po)}-phagotarsonemus. Pseudoplusia. Psyila. Scir\']iothrips, Spodoptera. Tetran}'chus. Tiialeurodes, Trichoplusia, for example in cotton, soya. \'esetable. fruit, citnii. wine and maize crops.
The formulations according to the in\'ention show bioefficacy comparable to tliat of coRA'entional EC formulations but at the same time avoids the use of large amounts of hazardous orsanic solvents and as such are more environmental and user friendly. The formulations ha\'e for a crop protection purpose an excellent crop-safety profile, i.e. they can be applied \\-ithout causing phytotcxic damage on crops. Low phytctcxicity is of importance and it is of special imponance when spraying on susceptible crops such as for instance j.:':"_e> crnan'Ciita i 1.".:: pz.;':..:., Ti.e rh} ;c;0\;o eivec"."_ ;;":c,"u-! > r\':rounced
accelerators) as is com.mon!y done in practice.
r'jf.her. the formulations significantly reduce the degradation of the
a,'ermectin(s) also when exposed to light.
Tjie forr'iulatious according to the invention have the follov.'ing chavacicrisiics; ,\ ■.-oiume-surface mean diaroetcr in [he range 0.05-20 fam. preferabi) 0.1-10 Li.n".. high tlash point and are v.hntc and free-lTowing (200-?.^00i"' cP./i.-iteterably .^CO--5000 cP depending on the particular composition of die fcnuulalioni foik.>-.\ ing preparation.
While concenmated fomiulations are move preferred as conur.ercialh. a^'adable goods, the ena consumer uses, as a niie. dilute compositions. Such dilute comDo^itions are part of the present invention. I

The invention is illustrated by the following examples:
Example 1
1,90 g Abamectin (94.00'^) is dis5ol\ed in 31 g solvent mix consisting of 17.9g meihylated fait}- acid lAgnique ME 890G). 7.1g n-octanol and 6.0g Shell Fluid 2613/8M. A total amount of 0.82 g of presen'ative. sticker and thdckener is added and dissolved. 60.8 g of aqueous phase consisting of a buffer agent. anionic emuJsifiers {6.3'?c w7w of the emulsion) and water is prepared. 'Ilie emulsification is performed in one of two ways, both resulting in an oil-in-vvater emulsion of comparable elective conductivity and volume-surface mean diameter of the emulsion droplets. 1) Under vigorous Stirling (3000--4000 ipm'i. the aqueous phase is added to the organic phase and stirring is continued until ihe volume-surface mean diameter is in the range 0.1-10 \im. 2) Under ■■ igorous

Uxampie Z
Oii-!;:-v, a';cr emulsions comprising Abaniec'in as active ir.greciicm -r.c ic;\ent ii7i\:^:res of r- ir.^clhyla.icd farty scid (Agiiique ME S9QG)- n-octano' ^nd jjioif b"li::d 2613/RM are prepared as described in exiimple 1 :it a range ct ]:.rl \-::ue> ?-;")c ihc ;i;.'b:li!v of the active ingredient in accelerated storage tests at 54^U ar.d ";'yC. ror 14 davs is determined, sec table 1, The composiiicn ('■"■^w/v^ ) of the sttidied em.uision is as follows; l^^r abamectin. 19.09!: Agnique Mb. iivOG. ~,;5';7- n-octano!. 6.4'S Shell fluid 26)3/8M. 1.0% preser\'ativc. andioam agent-sticker, thickener and citric acid. ~.07c anionic emulsiners ■ Soprophor R,K/D:spersogen LPS mixture) and water up to 100%. The formulation is divided in six and pH is adjusted usmg IM NaOH according to the pH ^-alues

indicated in table 1. The preparations appear as while non-transparent emulsions.
Table 1
Accelerated stability data for Abamectin oil-in-water using a methylated fatty add as solvent and octanol and Shell Fuid 2613/8M as cc-solvents at different pH values.

An oil-in-water emulsion comprising either Ivermectin. Emamecun bcnioate or Aversectin C as the active ingredient and various alkylated fatty acids, n-octanc: and Shell Fluid 2613/8M as solvents was prepared according \o table 2 applying tiie method in example 1 using premium grade of inerts and an ernulsifN'ing agent. The pH of the emulsion is adjusted to approxiinaiely 7 using NaOH and the storage slabiht-.' of the prepared emulsion is studied using accelerated storage tests at 54oC for 14 days. The preparations appea:' as white non-iransparenr emulsions. The results of the storage les'.s are given in table 2.

In a smiilarl}' performed dip-iest on 5. exiqua tlie prepaj-ed Emamectin benzoaie EVi'" ^hov r-d re>;;lt5 net sigP-ificantJy different to a commercial Emamectin
I Example 4 An /vhamcctin IS gA oil-in-water emulsion comprising Agnique ME 890 G. n-octarroi and Shell Fluid 2613/SM as solvenis and further auxiliaries was prcpaued m accordance with tlie ptocedure outlir.ed in example 1 usir:g premium grade ol" merfs. after preparation llie volume-surface niean diamieter was in the
I range 1-3 i.;m.
The emulstion was then treated m a high-pressure (uitensivei honiogcmzci, .-TJKI" the trcatir,e:U ".he mean diameter of the droplets \vas well below μm. The preT:aranon appar as a vvhne non-transparerjt emulsion.
) Example 5
Abam.ecri", IS g/i oil-in-"--^ater em.ulsions comiprising various soh'en: nhasj'S were pr^epared in accordance vidth the procedure outlined in example 1 using premium grade of inens. Solvents applied in the examples are chosen among Agnique ME 890G imethyl caprj-latei and Agnique ME :2C^F (C12 m.e:h>-l

coconats). Co-solvents applied include n-octanol, cyclohexanone and 1-hexanol, In all the formulations pH is adjusted to approximately 7 and for all
formulaiior.s the stability of the emulsion and the stabilitv of the acti^'e ingredient is high (accelerated storage for 14 days at 54°C). The preparations appear as white non-transparent emulsions.

Example 6 (compa:■a^i^el
AbaTT^ectni IS g/l oil-in-\vater emulsions coniaiinng variou? o;"; pliases and/or with \"aiiaiion of pH-vaiue of the emulsions ivere prepared in accordance wi;h the procediu"e outlined m example 1 using prerri:u:r. grade of inerts ana an optimal confbinatior. of en'.ulsifying agents in each emulsion produced. Oul\- the necessaiT amount of organic solvents was applied in order to keep the

Abamectin dissolved m the oil phase. The stimng speed during the emulsion formation was regulated such that the volume-surface mean diameter was in the range 1-20 )im after production.
Results are provided in table 5. and for the oil-in-water emulsions of compositions A through H the stability of the active ingredient is much lower than for oil-in-water emulsions prepared according to the present invention.

Example 7 (Comparative)
The stability of Abamectin in water at various pH-values and temperatures was determined. 194.4 mg of Abamectin was dissolved in 10 ml methanol and 1 ml of the solution transfen'ed to 100 m! of de-mineralised water and a 5 pan of this '^'as transferred to a buffer solution. The sample was kepi in the dark and the solution analysed using a HPLC. Results are provided in table 6.
Table 6
Degradation of Abamectin in v,ater at \arious pH-values and temperatures. 3 Buffer pH 4: Potassium biphthalate/NaOH: pH 7: Sodium phosphate/Potassium phosphate: pH 9: Sodium tetraborate.

Example 8 iComparative)
The stabi'it\' of Abamectin in vvater exposed to light al ^■arioli^ pH-\r;iu,--: was determinfc, 194.4 ins of Abamectin was diisoned :n 10 ml nv.":;iri;ri. and 1 iTij of the solution transferred to 100 ml of dem.;nerahsed \\TU'I" a.~c .■ part of this tiansfeiTed to a buffer solution. "Fhe solution was cxp^jsed u> jl^!-.-' (5000-6000 lux! at IS'^C and aual>'sed using a HPLC. Results are proMdcd in lable 7

Example 9
An oil-in-water emulsion formulation of Abamectin is prepared according to example 1. ri'ie com.positior! of the emulsions i.s as follows: 1 .S'Tr Abamectin. l7.4^c Agniquc ME S90G. 7.0% Octanol. 5.8":^ Shell Fluid 2613/8M. 2,S~^ presen'ative. ar.iifoam. agent sticker, thickener ar.d buffer 6-5 '~r losal of iw o anionic emulsificrs (Soprophor FLK and Dispersogcn LFSi and v. r-.ter up to
1 ml cf emiilsion is diJuSed tn a total volume ol" "iOO ml and 1 ml i^ trausfeneu to each of A cr\'stallisation bowls and left to dry in darknc'^:s, ■1\\ o bow]'; :;:-.-^ exposed to light m a Heraeus Suntest CPS unit ror a period of tvs'o iiuur-usin2 ~aximurr. effect and 'wc bov/ls are left in dai'l-:r;ess also for tvi'o hours -After exDosure the formulaiion residue is dissolved in lOmJ ethanol and the remaining amount of Abamectin is deierrriined by H.PLC analyses. The experiment is repeated using a commercial 13 g..T EC formulation e:

Abamectin for comparison. Table 8 shows the stability of the prepared emtilsioiii along with results from the conventional EC formulation of Abamectin. The table indicates that the stability of Abamectin under the exposure of light is greater for the emulsion prepared according to example 1 than for the comparative commercial EC formulation.

Abamectin 18 g/i oil-in-water formulations were produced according TO the description in e:on v..i;!-i i;-..-formulation described in Example J. The produced -Abamieciin !o s.-/. Ojl-i!\-v--;!^er lonniiia^ions were lested for phy:otoxiciiy on cucumbers Lvd !■'matOL-s Tracii'ional commercially a'.'ailablc .Abamecrm IS g/1 HC ■orrn.datioi'.i \v:=.i\-used as references in tlie tests, in some tests an cmuisitlablc imneja; uil (crop Oiri was applied on the planis together vizli the Abainec:;r rcrmul.T'icT..^, The percentage of leaf necrosis was used as the test parameter for ph\'totoxicit}'. For me tested 18 g/1 EC formulations, the leaf necrosis appeared a fev, days

Example 11
Field trials were conducted with oil-in-water formulation prepared according to the description in example I sho\^'ing that the EW and a commercial EC formulation had comparable efficacies in the control of citrus red mites {Pafion-vckus cirri) on orange trees, see table 10.
Table 10. Efficacy of Abamectin for the control of citrus red mite (Panonychus cirrij. The trial was conducted on 23 year old Washington' navel orange trees. Evaluations of live mites on 20 leaves per tree.
I 1 —~— i—■ ■ ■
Means vrithin a column followed by the same letter are not significantly
different iLSD, ij=0.05} after logio (x+l i transfoimation. Uniransformed
means ru-: listc.i, DAA - days after application.
llnde; liio repoitod field '.rial also the presence of the prcdaceous niiie Eiiseiii-: ;;^ir{ri.u-:i:. \--Has mo-'ritored. Results •■■howed no signifxarit difference bet'v'-eer. the effect of the commercial EC and ihe formulation prepai-ed accordu"!;^ to ihc present irr.'ention. se table ' 1.

Table H.
Effects of Abamectin on the pre...aceous mite, Euseius tularensis. The trial
was conducted on 23 year old 'Washington' navel orange trees. Evaluations
of live miles on 20 leaves per tree,

to description in example 1 showing that the EWs and a commercial EC
formulation hadcompaj"ab]? efficacies in ihe conti-ol of Psylla pyii hi pears in Italy, see table 13. In the trial a common miineral oil, Ovipron Top v/as used in a rviic- of 3f)0ml/hi of spi-d\ volurriC to furtlicr incrsaso efficacy ar-d pL--!."rai;on of the ac\i\c into the plants.

Table 13
Efficacy of an 18 g/1 Abameclin oil-in-water fomiulatioii used in field trials
compared to a commercial Abamectin EC product. Target specie was Psylla
pyri and the crop used was pear. The spray \'olume was 500 LTha/m tree
height. Results for a corventional Abamectin EC formulation are included for
comparison. DAA. = davs after application. The data is nrovided as efficacy
Exam.ple 13
Field trials using an Abamectin E\V formulation prepared according to
-j;-:.,_r:?.-r I '•■■i> :-:yyli>-:.'i i;:; si v .v^ :?~i-." :.r::r;; Terranychu'^ ypp. A ;o;al ci':
EW fonTiU^^atioii but vi-iih a soi\'eni chosen outside the scope of pi"esera mvontion did shew symptoms of phytotoxicity.
SiiTiiUu" tnals conducted on aubergine and tomato did not show sigiis of pli^^'totoxjc-t'/ for Abamectin EW formulations prepai'ed according to example 1. \i\ I'-iCSC ;i-:als a commercial Aba;-nectin EC fonrsulaticn used as compari^;ni-> ■ho^'.cd Hower droo, \\-hich inTeiferes with fi-uit developnien:. luu tni-, V, as "i.'i chserved widi EW '"."'rrnulations according to the pveit-m ir^-enuon, Iruilhir. uials in apples with Abamectin BW iorrTii!lai;ons acco'-dinE ■:■: the present invention sho\\ ed no phyiotoxicity.
Exauiuic !-■■
2.S6 2 .'\bamectii! i'~)A.Qi0^c>- is dissolved in 73.6 g solvent mix consisting ot
32.3 g ethyl caproate. 32.3 g n-oclanol and 9.0g Shell Fluid 2613/8M. A total
amount of 1,1 g of presers-ati\-e. sticker and thickener is added and diS50i\ed. 6-i.§ g cf aqueous phase consisting of a buffer agent, anionic em.ulsifiers , ''-'■

w/w o' the emulsion; and water is prepared, Emulsification is performed under vigorous stirring ('2000-3000 rpm), the aqueous phase is added to the organic phase and stirring is continued until the volume-surface mean diameter is in the range 1-20 μm. Adjustment of pH (pH 6-7) and viscosity when relevant is done following the emulsification process. The preparetion appear as a white non-transparent emulsion. The formulation is both physically stable {
heptar;oate cr cety! palmitate with n-octanol and Shell Fluid at elevated temperature above the melting point of the used alkylated fatty acids (30-40% of totalformulation), Abamction is added and dissolved as is preservative and sticker '60%of total formulation^ The v,'aicr phase is prepi^rcd consisting oi: buffer, emulsifier 7% if total formulation and thickner and scirred until homogeneous,. Enruisificalion is pcitormed under vigoromas sunning 2000 3000 μm aqueou.v ph^sc 15 ficded to 'ihe organic piiase and siirring is cont-.nued until the \"olume-siirffice mean diameter i-^ iii ihe range I-'IO Ltr., The teiuperature is io'Acred to room temperature and whtr: rele^-ain pIJ (pH 6 7] and visccsily is .adjcstea. The prepai"aiion appeitrs as v^ hite non-transparent emulsions. The preparation is both physically stable (K'i^'c phase separation v^her. stored a: 40-C; and chemicall;- stable and ha\'e physical-chemical Droperties similar to the formulation prepared according to example

AMENDED CLAIMS [received by the International Bureau on 19 March 2007]
], A concentrated oil-water emusion formulation for crop protection against pests, comprising
a) one or more pesticidal active ingredients sskcted among avermectins,
b) QHt; or more solvents selected among (CrC2Q}-aIkyl (Cs-C22)-fatty acid esters,
c) an emulsifier system comprising one or more surfactants, d) water and
e) one or more co-solvents having a solubility in water of less than 10% fi.t 2S=C, wh'i.-iib. The pH-value of fho emulsion is higher than 3 a;id the smonnt by ■/-■■--igl-it of cQ-solvem is ::cu2.i '-o or higher than the amount by weigh- of

3, :-■ "o-.rrnL:rr;^:ion accGmbi'i :T -j^y o?ihe claims 1-2, wherein ;hepH of tte O.O-:;.;KJ^V. ;;: betwefcii3 ;^n(' 12-
■-,. .- *".■'. ■"■"' ,.: :ioa acccr'i'Ug ",c (i.i',vn 3 fjirher comDrising one or mcv-' ril-
:J. ,', !v.:..-r:-r.'.]ai.io:i acco::d'"ri£ ro rtny of'.hs preceding ckmno 1 to 4. -,V;-;E;f;-^-, ri-j^
il-:::j.-mccixn.. EprjiomcQiin, ZvciTneeriri; hepimectin; Sela;i;cctirt, ;";i;vi:.ire3 mcrc-of nnd salts tharcof. I

6, A formulation according lo claim 1, whersin tbe sveimectdn is sslectsd
^inong Abamectin, Aversectin C and Bmamectin 'bemzaaie.
7, A formulation according to claiui 6, wharsin the aveimectin is Abamectin.
S. A form-ulation according ;o claim I, whsrein the com-ponent b) is selected grjiong allcyl eaters of fatty acids wherein the fatty acids have a cafbon chain lengih of 5-20.

13, A iC:.-.: ■^i'.^iic;:. ^c:,L)V;i;ng i.j c]au:i 12, ^.vherejn ths cc^T;pDaent b) is st'^^ct^td
14. A fojTtiulation according to claim 13, wherein the corapoiism b) is selected
amorig meihyi esters of laiity acids v,'herein ths latiy" acids have a oarbo::

15. A farm-UiatioB ascardingto claim 1, wherein the co-solvent is selected
eniong straight, branched or cyclic C5-CI2 aliphatic hydrocarbans, straight
or branched C5-C10 aliphatic alcchols, cyclic aliphatic ketones and ^neral
16. A formulation according to claim 15 wherein the co-soivent is selected
among straight oi branched C5-CI0 aliphatic alcohols and cyclohexanone,
opdonaily in combination with one or more minersl oils,
17. A ibj-mulatioii according to clat>n 16, whereia the co-solvent is selected
_ ftmcng hsxanol and octanol optitsnally in con:bination with one or more

2S. A method according to claim 27, wherein the formulation. is applied in diluted farm.
29, A method according to claim 28, wherein the formulation is applied to plants or plant seeds.


3058-CHENP-2008 AMENDED CLAIMS 25-09-2013.pdf


3058-CHENP-2008 CORRESPONDENCE OTHERS 21-11-2013.pdf

3058-CHENP-2008 CORRESPONDENCE OTHERS 24-12-2012.pdf

3058-CHENP-2008 FORM-3 25-09-2013.pdf

3058-CHENP-2008 OTHER PATENT DOCUMENT 25-09-2013.pdf

3058-CHENP-2008 POWER OF ATTORNEY 21-11-2013.pdf


3058-CHENP-2008 OTHERS 25-09-2013.pdf

3058-CHENP-2008 POWER OF ATTORNEY 25-09-2013.pdf

3058-chenp-2008 abstract.pdf

3058-CHENP-2008 AMENDED CLAIMS 16-12-2013.pdf


3058-chenp-2008 claims.pdf

3058-chenp-2008 correspondence-others.pdf

3058-chenp-2008 description(complete).pdf


3058-chenp-2008 form-1.pdf

3058-chenp-2008 form-18.pdf

3058-chenp-2008 form-3.pdf

3058-chenp-2008 form-5.pdf

3058-chenp-2008 pct.pdf

Patent Number 259101
Indian Patent Application Number 3058/CHENP/2008
PG Journal Number 09/2014
Publication Date 28-Feb-2014
Grant Date 25-Feb-2014
Date of Filing 18-Jun-2008
Name of Patentee CHEMINOVA A/S
Applicant Address P O BOX 9, DK-7620 LEMVIG
# Inventor's Name Inventor's Address
PCT International Classification Number A01N43/90
PCT International Application Number PCT/DK06/50068
PCT International Filing date 2006-11-17
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 PA 2005 01619 2005-11-18 U.S.A.
2 60/738,072 2005-11-21 U.S.A.