AU2013206347A1 - Spray droplet modifier composition - Google Patents

Abstract

The invention relates generally to oil-based liquid concentrates or use in agricultural applications. The invention relates more particularly to formulations that comprise an agen that modifies the Viscosity of a sprayable liquid containing the formulation, oil and a dispersing 5 agent.

Description

I AUSTR ALIA Patents Act 1990 COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED Spray droplet modifier composition Applicant Caitex Australia Limited The invention is described in the following statement Spray droplet modifier composition Field of the invention The invention relates general to oil-based quid concentrates for use in agricultural application, The inventionrei'ates maore particularly to formulations that compose an agent that 5 modiles the viscosity of a sprayahle liquid contaiinng the formulaon, oil and a dispersing agent. Background of the invention ]n the agrochemical industry agrieulturally-active compounds arc often sprayed, normally after dilution in an aqueotu spray hqcid onto plants and/or their habiat. When the 0 agricultural sprays are to be directed onto a specific target the aerial spray or discharge delivery systems are typically mounted on airplanes, tractors, or ground rigs. Vhen applying such fotrmulations, a more or less pronounced drifting of the syray solution conainintg the active substance(s) may be observed depending on the wind condition nocle type, and other application parameters such as nozzle pressure, spray boom height and length and vehicle speed. 15 The difft of a spray is determined to a great extent by the droplet size ditniumion of the S ray Mist or the fine partides-end of the droplet-size spectnmt in agricultural sprays (ie. those less than about 150 pm in diameter), contributes most to drift. While small droplets provide better coverage of a target, much of the active chemical ingredienus in a spray can be rendered ineft'ctive or lost due to spray drif because of the inabiity of the small diameter spray or mist 20 particles to reach and impact upon the intended target (ie the crop or field locus Ginerally. the snmialr the droplets the longer the residence ime in the air and the higher the tendency to evaporate and/or to drift rather than deposeitiin the id borders-. In addition, the dR of certain agriculturall-active agents such as pesticides, is a major source of concern in relation to the environmental impact of agriculture on natural ecosystems 25 and urban areas. Tis T drfting material night cause damage to neighbourng ops. and have eftbcts on the local enviroment (e.g. surface water, non-arget fora and fauna) as well as bystanders and occupants in residential areas. Accordingly, there is a need to reduce these drift induced problems associated with agrochemicalppication.

Various methods arc used to prevent the drifting of the spray oddethe field borders. The use of natural or ariiial windbreaks is ell known. However it has been described that even when such screens are used, drift can cause deposition of the ative substances behind such borders (eg. Schanpheleire, N. e aL Deposition of spray drib behind border structures Cop 5 Protecaio (2009) 28 1061 1.075). Another fequentlyused drift mitigation measure is bulkr zones. either off-crop or in-crop. A disadvantage of off-crop buffer zones is that part of the field cannot be sown with a crop, an economic cost to the farmen A disadvantage of in-erop buffer zones is that part of the crop is not protected adequately, resulting in a lower yield and perhaps resistance development. Clearly, this is something frnmers want to prevent. 0 Next to physically limidng spray dft (eg. using spray shields , it i also possible to alter the structure of the spray cloud so that less drops are prone to drift (ie,. typically those drops under 150 In). This can be done by choosing different types onozzles, changing the pressure at which the spray cloud is produced, or by changing the properties of the spray liquid itself. Changing nozzles andlor nozzle pressure is something farMiers do not prefer to do because it is .5 time consuming and is an added cost to crop production. Also, the equipment needed on a sprayer to deal with variable: apicaion rate is not common, For, these reasons. a more acceptable way to optimise a spray cloud so that it generate ales drift is by adjusting the properties of the spray liquid. One solution proposed in the art to reduce mist and chemical drfin aqueous agricultural 20 sprays is to incorporate into the aqueous medium a viscosity modifier, The viscosity modifier increases the average droplet size of the spray cloud by increasing the viscosity of the spray sAluon Examples of some cominerciall-availabl products that contain viscosity moditiers (whkh can be added as tank mix adjuvants wih pesticide fbrmnulations) include Dmp Zone DC, Pointblani Nalco-troh and sta-Put 5 from Helena, and AndDrift front AmegA Science 25 Inc. in addition. several patents have been published that discuss the use of viscosity modifiers to reduce drift (eg.US 7341981 and US 6358296). However, there is a tendency for viscosity modifiers tocreate extremely large droalets.ns well as reducing the fraction below 150 am when atomising liquids through conventional agricultural hydaulic nozzles. Retention of larger droplets on leaf surfaces may be reduced as 30 the larer droplets are more likely than smaller droplets to run-off, bounce, or shatter and 4 redistribute to soil. Fewer larger droplets adhering to the leaf surface. will reduce overall biological efficacy. One of the most commonly used viscosity modifiers is guar gum, or its derivatives. Guar gum is traditionally used as a solid additive to an aqueous agricultural spray medium. Although 5 guar gum is often referred to as a cold water swelling polymer it hydrtes in eitheold or hot water to give high viscosity solutions The viscosity development depends, to a certain extenton particle size, pH and tenperanure. Guar gu solutions are stable over the pH- range of 4A0 to However, the aqueous hydration of dry, water-soluble polymers such as guar gum and/or 0 its derivatives in an aqueous aricultural spray medium in order to realize drift reduction properties can ofen be an arduous and frustrating task tor the end-user Insuficient dispersion of pmdered guar gum, caused most often by th wtoo rapid addition of the powder to the aqueous medium, or insudicient agitation of the medium during the guar gun addition process, often results in agglomeation or lumps of guar gel. The lunps of guar gel or other inhor ogeneity of * the mixture can result in difficulty in spraying and loss of drift con rol, Ihese gel lumps not only cause a lowering of the overall conections of dissolved guar gum in the spray mdium and therefore a reduced. drift cmtrol of the medium. but alo result ina medium thatil not flow or be readily pampable and result in plugging of the spray nozzle holes. The agglomeration can be reduced in many cases by adding the guar gum to the aqueous 2) system very slowly with vigorous agitation. Slow addition, howeversubstantMiy reduces the efficiency and speed of the end-user's processes. For the above reasons, agricultural end-uses, such as fhrners continue todesire a fast, effective and simple way of incorporating viscosity modifiers into their agrochenical fonnulations, 25 Other components of agmchemical compositions such as non-inic surfactants, crop oil concentrates and silicon superwetters while possibly improving the efficacy of the herbicide solutions to which they are added, actually increase the drift risk of the spray cloud thus produced because they lower the dynamic surface tension of the spray liquid. This extends the pray sheet* expressed fiom the nozzle, which breaks up further from the nozzle, thereby 30 producing many more fine droplets.

5 In addition, traditional spray ois and crop oil concentrates can have a negative impact on the performance of special drift reducing nozzle (e g air inclusion oir induction nozzles) that are being increasingly used These special drift reducing nozzles produce larger droplets with entrained air bubbles, which act as cushions when the large droplets strike their target, thereby 5 reducing droplet rebound. it has been proposed that traditional spray oils and Crop oil concentrates reduce the air entrapment in these large dropets thereby increasing likelihood of rebound from the leaf targethich reduces the efficacy of theactve. Based on the described market demands - good efticacy but limited drift - there is a need for formulations to be developed that can reduce drift without ncgatciely affecting the biological 0 performance of the formations. Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment or any form of suggestion that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and igarded as relevant by a person skilled in th at. 15 Summary of thi invention 1l'he present inventors have surprisingly found that, by including significant amounts of oil in a formulation containing an agent that modifies the viscosity of a sprayable liquid containing the formulation, a concentrate can be obtained that significantly reduces the drift of a sprayed liquid containing the oil-based concentrate during spray application, reduces or prev ents 20 the undesirable agglomeration of the agent, and maintains or even improves, the efficacy of agriculturally-active compounds apphed with the formulation. As used herein, a viscOsity-modifying agcnf' is not intended to encompass or include one or more agents commonly used as thickeners. The term Misosity-modilying agent" is intended to refer to an agent that modifies (e.g. increases) the viscosiy of a tank mixture or 25 sprayable liquid to which the viscosity-modifying agent is added t is not intended to refer to, or to include, an agent that affects the rheology of the oilbased liQuid concentrate itself This is discussed in uore detail below. The present invention relate on oil-hased liquid concentrate composing: 6 about 0.01 to about 15% w/w of al, agent that modifies the viscosity of a sprayable liquid containing the oilbased liquid concentrate; and 56 to about 75% w/w ofoil selected from vegetable, paraffin; mineral and synthetic oil and mixtures thereof In one embodiment, the v iscositynodif'ing agent is present in the concentrate in an amount of about 0.5 to about 10% w/w In another embodiment, the viscosity-modifying agent is present in the concentrate in an amount of about (0 to about 5% w/. Preferably, the amount of the viscosity-mnodifying agent in the concentrate is about 5%w/w a fying agent is an organi poyerCh In a preferred embodiment, the viscosi -inodi an olme, The 10 organic polymer may be a polyacrylamide, a polyethdlene oxide, a polvvinlpvrroiidone) or a guar gum and/or its derivatives(and mixtures thereof) Preferab, theviscositymodifyingagen is a guar gum selected frorn the group consisting of non-derivatized guar gum, no-cationic derivatized guar gwn, cationie guar gum, and mixtures thereof In one embodiment, the oil is present in a amount of 56 to about 5% w/w. In other 15 embodiment, The oil is present in an amount of 56 to about 60% w/w. Preferably. the amount of oil in the concentrate is about 60% w/w (e g. 58% w/wb The oil may be a mixture of a vegetable oil and a paraffin or mineral oil Preferably, the weight ratio of vegetable to paraffin or mineral oil in the oil mixture Is about 12 The oil-based liquid concentrate of the present irention may also comprise a dispersing 20 agent, Accordingly, the present invention also relates to an ofl-based liquid concentrate coprisi ng: - about 0.01 to about 15% w/w of an agent thatmodifies the viscosity of a sprayable liquid containing the oil-ased liquid concentrate; 25 -56 to about 75% w/w of oil selected from vegetable, paraffin, mineral and synthetic oil, and Mixtures thereof; and - about 1 to about 5% w/v of a dispersing agent in one embodiment. the dispersing agent is present in the concentrate in an amount of about 2% wv/ Mn one embodiment, the oil-based liquid concentrate consists of: about 00 1 to about 15% w/wnf an agent that modifies the viscosity of a sprayable 5 liquid containingthe oil-based liquid concentrate and 56 to about 75% w/w of oil selected from vegetable, panafn, mineraand synthetic oil or mixtures thereof. ihe oil-based liquid concentrate may also consist of - about .001 to about 15% ww of ran agent that modifies the viscosity of a spravable 10 liquid containing the ol-based iquid concentrate: 56 to about 75% w/w of oil selected froi vegetable paaffin, mineral and synthetic oll, or mixtures thereof; and - about I to about 5% w of a dispersing agent In another etmbodiment, the oi-based liquid concentrate consists essentially of' 15 - about 0.01 to about 15% w"W of an agent that nmodifies the isposity of a sprayabe liquid containing the ol-based liquid concentrate; and - 56 to about 75% ww of an oti selected from vegetable, paraffin, mineral and synthetic oiLer mixtures thereof Thbe oil- based liquid concentrate mayaso consist essentially of 20 - about 0.01 to about 15% ww of anagent that modifies the viscosity of a spravable liquid cntang the oi-based liquid concentrate - 56 to about 75% wv of an oil selected from vegetables paraffin, mineral and synthetic oil, or mixtures thereof; and - about 1 to about% w/w of a dispersing agent 8 In another emsbodiment, the oil-based liquid concentrate further comprises one or moTe additonal agents selected from surfactants, envisifiers. PH stablsers ora wetting/spreading agents, and mixtures thereof The surfactant may be ionic. nofnionic, amphoteic or zwitterionieor a mixture thereof S In one embodiment the surthtant is present in the formulation in an amount of about 20 to about 40%Wiw (eg about 37% w/wY In one embodiment, the surifactant is a mixture of orie or more toionuic one or more ioni and one or more amphoteric surfactant In this embodiment, the ioni surfactants are present in an amount of about I to about 5% w/w (e g abu in3% w3 the amphoteric 0 surfactants are present in airamount of about 10 to about 30% w/w (e.g about 20% Ow) and the nonionic surfactants are Present in an amount of about 10 to about 20% w/w (eg. about 14% w/w). In one embodiment, the emulsifier is present in the formulation in an amount of about 5 to about 15% w/ (eg. about 10% w/w). 1i 11 one embodiment, the i stabilizer or acidifing agent is present in the formulation in an amount of about 01 to 10% w/w. The pH stabiLiser may be present in an amount of about 0, 1 to about 5% w/w (ci-gabout 3% v/w-). In one embodiment. the wettingispreading agent is present in the formulation in an amount of about I to about 1 0% w/wA Ire wetting agent may be present in an amountof about I 20 toabout % ww (e.g. about 2% w/w). In one embodiment, the oil-based liquid concentrate does not comprise one or more thickening agents. The present invention also relates to a drift-reducing sprayable liquid comprising an aqueois solution, and, dispersed in the aqueous solution, an oil-based liquid concentrate 25 comprising about 0.01 to about 15% w/n of an agent that modifies the iscosiy of the sprayable liquid, 56 to about 75% ww of oil selected from vegetable, paraffin, mineral and sy nthetic oil, or mixtures thereof. and about I to about 5% ww of a dispersing agent, wherein the oil-based liquid concentrate is present m the aqueous solution in an amount effective to reduce the drift of the sprayable liquid, 9 In one embodiment, the drifteducing sprayable liquid further comprises one or more agricuturalytieive compounds. Examples of suitable agdcultural actie compoumds include fungicides, bactericides. insecticides, acaricides, nemnaticides. noluscicides. herbicides, safeners. plant growth regulators, plant nutrients, biological and repenents. S [he present invention also relates to use of an oi-based liquid concentrate comprising: - about 0.01 to about 15% wiw of an agent that modifies the viscosity of a sprayable liquid containing the oilbased liquid concentrate; - 56 to about 75% w/w of oil selected from vegetable, paraffin, mineral and synthetic oil, ormixures thereof; and 10 - about I to about 5% w/w of a dispersing agent, for the reduction dung spray application, of ie drift of the sprayable liquid containing the oil abased liquid concentrate. The present invention also relates to an oil-based liquid concentrate comprising: about 0.01 to about 15% w/w of an agent that modifies the s vicosity of a sprayable 15 liquid containing the oil-based liquid concentrate; - 56 to about 75% w/wt ofan oil selected from vegetable, paraffin, mineral and synthetic oil or mixtures thereof and - about 1 to about 5% w/w of a dispersing agent. when used for theducion, during spray application, of the drift of a sprayahie iuid 20 containing the oil-based liquid concentrate In one embodiment, the spayabie liquid contains at least about 0,000001 to about i10 v/ (egabout 0.00005 to about 2.5% vV) of the oil-based liquid conentrate, based on the weight of the spray liquid. Preferably, the amount of onentrate in the sprayble liquid is about 025% /v. T he sprayable liquid may also contain additives. 25 In one enbodiment, the sprayable ligid further comprises one or more agriculturay active compounds (as discussed above) t0 The oi -based liquid concentrate may also contain water In this embodiment, the liquid concentrate comprises about'00001 to about I0% wAv (evg, about 0.00005 to about 0.5% w/) watei The present invention also relates to a method of making a sprayable liquid foruation 5 forgagrochemnial application comprising: - providing an oil-based liquid concentre comprising about 0.01 to about 15% w n of an agent that modifies the viscosity of the sprayable liquid formulation, 56 to about 75% wlw of ol selected from vegetable, paratin. mineral and synthetic oil, or mixtures thereof, and about I to about 5% w/ of a dispersing agent, m an amount effective to reduce the drill of the sprayble 0 liquid providing an aqueous solution; and combining the oil-based liquid concentrate with e aqueoussolution; to fon a d payable liquid formulation. In one embodiment, the aqueous solution comprises one or more agriculturaily-actie *5 compounds, In another embodiment, one or more agriculturally-actve componds are added to the sprayable liquid fortalatkmntollowing the combining step. Further aspects of the present invention and further embodiments of the aspects described in the gparagraphs will become apparent from the following dec ription, given by way of example. 20 Detailed description of the embodinments The present invention reLates to an oil-based liquid oncentrate comprising: - about 0.01 to about 15% w/w of a gent that modifies the viscosity of a sprayabie liquid containing the ol -based liquid concentrate: -S6 to about .% w/iw of an oil selected (tom vegetable, paraffin, mineral and synthetic -or mixtures there; tand -about I to about 5% w/w of a dispersing agent II As mentioned above, the present inventOrs have iound that. by including significant amounts of oil in concentrates containing viscositymodfying agents, a liquid concentrate fonnulation can be obined that significantly reduces the drift of a spraynbliquid containing the oilbased concentrate during spray application, reduces or prevents the undesirable Sagglomeration of the viscosity modifer when diluted to form the sprayable liquid, and maintains, or even improves the efficacy of agreulturallyaacie onpounds applied with thee ncentrate. It has been unexpectedly found by the present inventors that a liquid concentrate, compsngm an agent (such as guar gums ann/or derivatives) thereof) that modines the viscosiv of a sprayabie liqud to which is added and a substantial portion of a hydrophobic component 0 (the <il can be foed, and that such a concentrate is an effective iscosity modifier of a sprayahle liquid to which it is added, as wel as beidg stable over extended periods of time. his is surprising, because before the present invention, it was understood that a number of hydrophilic agents (such as guar gums) commonly used to modify the viscosity of sprayable formulations could be used as viscosity-modifying agents in solid-, granular-, dust- or powder 15 type fornulations. However, t was akso understod that these more hydrophie agents could not be formulated in oilbased formations because it was thought that, in those formulations, such agents would not form stable formulations As discussed below, it is the hydration of a number of these types of agents that is responsible fr their viscosit-modifying properties. Therefore, prevention of premature hydration is a desirable property of the liquid concentiae fonnultion. 20 The present invention has shown for the first time that a stable liquid oil dispersion can be used as a fornmulauion for viscosity-modifying agents such as guar gums. As can be seen from Example 4, the liquid concentrate of the iesent invention can be stored for long periods of time under normal storage temperatures while still maintaining its formulation stability and activity. One example of a viscosirymodifying agent foi use in the present invention is guar, 25 which activates (hydrates and swells) when mixed with water. Temperature and pH! extremes limit this action In the concentrate of the present invention, guar is dispersed in the oil using dispersing agents to prevent prenature activation. In addition in the present invention, the use of thickeners can be avoided Thickeners such as xanthan gum, clay compounds or surftetants with viscosity-affecting phase behaviour) 30 are used in suspension concentrates where a solid active is insoluble in the formulation diluent, The thickener prevents the active from settling by increasing the vsosity of the concentrate.

12 Accordingly, thickeners are used as inert ingredients that aid formulation stability (or "shelf lif&). The agent used to modify the viscosity of a sprayabie liquid in the concentrate of e present irvention in fact reduces the viscosity of the concentrate hickeners are therefore different to the agents that modify the viscosity of a sprayable liquid containing the oi-based S liquid concentrate that are contemplated in the present invention. The property of viscosity modification of the sprayblie quid mixture is not related to the formulation stability aspect aided by thickeners The viscosity-modifying agent used in the concentrate of the present invention acts on the Viscosity of the sptayable mixture by swelhng when it comesnto contact with water By increasing the viscosity of the sprayable minxure the vscosiyodifying agent 0 modifies the size of the droplets of the sprayable mixture formed by a nozze Therefore, in one embodiment, the ol-based liquid concentrate of the present invention does not include one or more tckening agents. but does include an agent that modifies the viscosity of a sprayable liquid containing the ilbased liquid concentrate (Ki a viscositymodifying agent). Once in a sprayable mixture. the normal mice!lisation associated with emulsions, 15 combined with the steric hindrance action ofhe dispersing agents of the emulation combine to markedly reduce the rate of hydration after an initial gtar activation period. Without wishing to be bound by any theory or mode of action, the present inventors believe that since the process of hydration is both pH] and emulsifying tendency dependent, the concentrate of the present invention is particularly useful because it has been optimised so that 20 the final viscosity produced in the spra'able tank mixture can be controlled, to a certain degree, andi in this way the tendency to form fine droplets can be controled mre precisely. 'This is particularly the casewhen a guar-based product is used as the viscosity-modifyng agent, which is more commercially acceptable than other viscosity-nodifyng agents In addition the viscosity-modifying agent is more effective than expected at the low 25 amounts of use in the sprayable liquids. For example, a standard recommended dose of guar gum for use in sprayable drop modifer compositions is 06 gL (8 on 100 gal) In contrast, the concentrate of the present invention allows the use of only 0.21% v/ in the tank, which is equal to 0.12 g This amount of viscosty modifier is tve times lower than the currently recommended, standard dose of viscosiy modiftier for use in sprayable fonnuladons. However, 30 the concentrate of the present invention is more effective than the viscosity modifier compositions currently on the market.

13 Ihe present inventors have found that the concentrate of the present invention reduces the percentage of droplets in the drifiable" range (ess than 150 pun diameter) by up to 50% from most spray nozzles. This can be seen fRom Table 2 where the concentrates of the present invenion have been tested against different tank mixtures and nozzles. Further, the concentrate 5 of the present invention can be made up easily into a spayable foraulation using standard procedures. without adversely affecting the rheological properties of the resuling sprayabie formulation. typical polymers useful as drift reducton agents (e viscosifvmodifying agents) include organic polymers such as he polyacrylanidesn the polyethylene oxides, the poly(vinyl 10 pyrrolidones) and guar gum and/or its derivtve, gatine and the like. Currently polyacrylamides are the most commonly ised drift reduction spray tank additives in agriculture. However synthetics such as the polyacrylanrides have inherent drawbacks. For exarip.& they are usually distributed in organic carriers, which limit the dipersibility and additionally ia present a volatile organic component problenfr the end user The polymers themselves are 15 essentially non-biodegradable and therefote it would be highly desirable from an environmental viewpoint to reduce their usage, Furthermore, these high molecular weight synthetic polymers are extremely sensitive to shear stresses, The high shear degradation of the synthetic polymers often realizes a significant decrease in solution viscosity over time which result, in spray processing in a lessening of the droplet-size distribution control effects. 20 In summary, synthetic polymers, Such as the olyacrylanides have several major characteristics that are not conducive to ease of use or reliable efficiency: difficult dispersibility, low biodegradability, and shear sensitivity Natural guar and its derivatives, under controlled conditions, fuactimon as exceent drift reducing agents with essentially none of the above-identified disadvantages associated wih 25 synthetic agents such as the polyacrylamide agents Guar gum is the refined endosperm of the legume seed of guar beans, a plant which phyicaly resembles the soy plant, '[he gum is a pure food vegetable colloid recognized by the agricultuI, chemical and food formulation industry for many years as havig excellent film forming and stabilizingproperties 14 Functionally, non-devatHzed guar gum is a told water swelling noninic poiysacchaide which develops and maintains its properties over a wide pI range. The guar polysaccharide is a complex carbohydate polymer composed of essentially a straightchain of mannose units with singel-inembered galactose branches, chemicallyclassiIed as a polygalaetomannan. 5 Guar solutons or dispersions are sinply prepared by rapidly sifting dry gum into a vigorously agit-.aed tank of wateJr armd peritinig the gun to hydrate. Hiher %wtr temperatures can shorten the hydration time so long as the heating is not so prolonged or xessive as to degrade the polymer. At concentrations used in this invention it is believed tha solutions or dispersions of 0 guar essentially have a zero yield value i. they begin to 1ow at the slightest shear. The nature of guar allows almost constant viscosity for a given soliion coneentratiin over the p1 range of 3 to 10, Above pt1H a lower viscosity results from the decreased ability of*le gum to hydrate. The opLimuin hydration range occurs between pH 5 and 8. This unusual ofnyaiift ofgennhecntueo h compatibility of guar over the 3 to 10 PH range is attributed to the non ioic nature of the .5 molecule Etherification and esterification reactions are made on the guar hydroxy functionalities The (6 hydrax position is the most reactive position for etherification, for example with propylene oxide, but the secondary bydroxyls are lso prObable sites. Principle etherification reactions are carboxynethylation ria mnonochoroacetic acid, 20 hydroxydakylation Via ethylene oxide or propylene oxide and quatenization with various quaterary amine compounds containing reactive epoxide or chloride sites. Anionic and canonic sites modify the way the guar molecule imeracts with inorganic salts, hydrated cellulosic and mineral surfaces, and organic particulates. In general, the hydroxyalkyl ethers of polygalactomrannans are prepared by reacting the 25 polygalactnmannans with aikylene oxides underbasic conditions In US 3723408 and 323409 guar flour is reacted with alkylene oxides in the presence of water and sodium hydroxide. The reaond rodtis then nualized wth acid, aed nT an alcoholnvater mixture ared ean drid and ground In US 3483121, th'oyaatmnasand the alkylene oxidesQ" are- reacted under basic conditions with small amounts of water and larger amounts of water miscible or water inmd scible organic solvents Specific hydiroxylkylating agents include ethylene oxide ;2pmpylene oxide, I,2 butylene oxide. Whexylene oxide ethylne ehlohydri propylene chlorohydrin and 5 epichlorohydrin. ydroxvpropylation increases the gun' soiubiity resultinTIg in a product that hydates rapidly. regardless of water temperature. ydroxyalkyl derivatives are more tolerant of the water-miscible solvents and therefore can swel in and develop viscosity in aqueous sohlons containing low maecular weight organic solvents such as methanol and ethanol Both 0 hydroxyAl and carboxymethyl derivatives typically borm clearer solutims than standard non derivatized guar gu anad also hydroxy yalkyl dernvativsrsist thermal degradation better than non-den vatized guar. Eydroxypropyl guar gum is particularly useful as a Vow modifier and frtion~w reducligagenit, whch does not floccul~ate solds and is the most preferred derivatize-d guar gum of this invention. Carboxyalkyl ethers amd nixed catboxyhydroxyaikyl ethers of polygalactomannans are described in US 3740388 and US 3723409. respectivy.hese derivatives are made by reacting the poiygalactomannan with the derivatizing agents (halofatty acid and alkylene oxide) in a waier-acohol mixture followed by washing with water-alcohol mixt urges. Specific carboxyalkylating agents include chloroacetic acid. chloropropionic acid. and 20 acrylic acid. Carboxymethyltion introduces an anionic function to the polymer chain and further increasesthe soiubiliy of guar gun. Carboxymethyl hydroxypropyl guar gum is exceptional in its ability to suspend undissolved solids. Other derivatives of polygalactomannans are described in such patents as US 246502 25 (cyanoethyl ethers) US 4094795 (diakylacrvlamide ethers) and US 3498912 (quatemary amonauwm alkyl ethers). in the described processes, the reactions are conducted in water organic solvent mixtures and the reaction products are washed with solvens of water solvent mixtures, Specific quatenar amimonnun alkylating agents are such agents as 2 3-epoxypopyl 16 'rnthylammonium c horide. 3chloro-2 hydroxypropyl trimethylammonium chloride and the like. Grafted guar derivatives may be formed by the use ofgrafting reactions, and these products may or may not also be derivatized using the methodologies herein described. Other agentsthat can react with the hydroxyl groups of the poygalactoimannans to form ether groups are, fr example, alkylatng agents which include methyl chloride, methyl bromide ethyl chloride, ethyl iodide and isopropyl chiide; aminoalkylating agents such as aminoethyl chloride, aminopropyl bromide, and N9dimethylaminopropyl chloride; thylenically unsaturated group containing agents, which react through Michael addition with hydroxyl 0 group, such as acrylanide, ethacrylamide acrylonitrile, methacrylonitrie acrylic acid, sodium acrylate and, in fact, any of the polymerizable nonomers vhich contain one ethylenically unsaturated polym.erizable group, The term "derivatized guar" is meant to indude any of the above described derivatized guar gum products. 15 Non-derivatized guar gum derived froi a nitrogen-fixing, renewable resource, is a versatile environmentaly friendly, highly biodegradable polymer. Derivatized gIuar ums are slightly less sensitive to biological degradation, as the molecules are less suitable as food for common organisms The viscositymodifyig agent of this invention, which is selected from organic polymers 20 such as the polyacrylamides, the polyethylene oxides, the poly(viny pyrrolidones) and gnat gum eg nonderivatized ga gum, noncationic derivatzed guar gum. eationie gtar gum, and mixtures thereof gelatine, and derivatives and mixtures thereof is present in the concentrate in an amount of about 0.1 to about 1 5% w/w (e.g. about 0,5 to about 10% whwi In another embodiment, the viscositymoditying agent is present in the concentrate in an amount of about 25 05 to about 5% w/w. Prefirably, the armount of the viscosity-nodifying agent in the concentrate is about 5% wOW The derivatized guar preferably has a molecular weight of from about 50,000 g mo! to about I0,000,000 g/moL preferably of from about 200,000 g/mol to about 5000000 g/mol and more preferably of from about 1L000.000 g/mol to about 5000,000 g/mot Examples of f7 deriuized guar gum suitable for use in the concentrate otthe present invention include Ag-Rho DR 2000 (a hydroxypropyI gua marketed by Rhodia, the oil-based liquid concentrate of the present invention also contains oil selected from vegetables paraffin, mineral and synthetic oil, or mixtres thereof The oil is typically present in 5 the conrate in an amount of 56 to about 7$?'t ww. As used herein ranges (such as I to 10% w/w and C 0 C) are intended to specify and include allrang, as well as the individual numbers within that range. For example, the range of 1 to 10% /xw includes ranges such as 1 to 2%, 3 to 5% and 2 to 7%wv, as well as specific amounts, such as 1% Ow 2% w/, % w/y 4% wAw,5% w/%, 6% W/ 7N w/wM 8% w/w 9% 0 w/w and 10% w/w, As used herein, except where the context requires thewise, the term comprise" and variations of fiie term, such as "comprising, "comprises" and "compised, are not intended to exclude further additives, coimponents, integers or steps. Suitable vegetable oil are generally known and commercially available The term 15 "egetable oils" is to be understood as including, for example, oils from oleaginous plmt species, such as soya bean oil rapeseed Oil., maize genn oil, maize kernel oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, this oil, walnut oil arachis oil olive oil or castor oil, clza oil and canola oik Canola oil and its derivative methyl olcate, and mixtures thereof is particularly preferred. In the case of triglycerides, esters of CwC and C-Cjcefatty 20 acids of glycerol are preferred. The C lCaty acid esters of glycerol are fbr exanp esters of unsaturated or saturated C 1

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2 fatty acids, in particular those having an even number of carbon atoms, for example erucic acid, lrie acid, palmitic acid, and in particular CGefatty acids, such as stearic acid, 0oel acid, linoleic acid or inenic acid, Suitable mineral oils are various commercially available distilate fractions of' mineral oil 25 petroleum). Preference is given to mixtures of open-hain C 4 C30hydrocarbons, cyclic hydrocarbons (naphthenes) and aromatic hyaodrocarbona The hydrocarbons can be eiher snraght chain or branched Partar preference is given to mixtures having an aromatic portion ofless than 8% by weight Veryparticular preference is given to mixtures haing anaromati portion of less than 4% by weight iS Suitableparaffin oils are stright-chain and branched ( ~Ct hydrocarbons. Paraffin oils are also known as base oil or white oil and are commercially availae, for example.as Bavol@ 85 (Exxon Mohil Machelen, Blgium4Marcol® 82 (Exxon Mobil, Machelen, Beigium BAR 002 (RA;M21) SpA, Naple aly, Pionier 0032-20 (Hansen & Rosenthal KO, Hamburg 5 Germany) and Kriszol M 14 (Carless Surrey, England); Suitable synthetic oils are various comen rcially available oils that are artificially produced from chenicaliy-nmoditied petroleum components or other raw material eg. hydorckehydrisomerized semi-synthetic or synthetic base oil belonging to API Group IU such as Nexbase 2002 (Neste Oil, Belgium), Poly Alpha Olefins (POAs) belonging to API 0 Group IV, and API Group V base oils including synthetic esters The oil may be present in the concenitate of the present invention in an amount f 5i6 to about 75% w/w (eg g6 to about 60 yAvy Preferably, the amount of oil in the cnentrate is about 60% wv (eg. about $8% x/w). The oi in the concentrate may be a mixture of a vegetable oil and a paraffin or mineral 1 oil. Preferably, when the oil is a mixture of vegetable and paraffn oil the weight ratio of vegetable to paraffin or mineral oil in the oil niixtue is about 1:2 The dispersing agent may be present in the concentrate of the present invention in an amount of about I to about 5% w/w tog. abt 2% "/) 0 The dispersant will be present in n amount to facilitate the separation of particles of the viscosity-modifying agent and to prevent 20 settling or clumping thereof Possible dispersing agents that nay be included in the concentrate of the present invention are all substances of this type which can customarily be employed in agrochemical agents. Siabl dispersing agents include nonionie agents such as linear and branched alcohol alkoxylates and alkyl phenol alkoxylates, and anionic agents such as phosphate esters and derivatives of suiphonie acids. The dispersing agent may be a mixture of various 25 dispesing ages, including mixtures of anionic and ionic agents. The oilbased suspension concentrates according to the invention may furher comprise one or more additional agents selected from surthetants, enusiters pH stabilsers or acidifng agents, dispersion and/or wetting/spreading agents. and mixtures there A person skilled in the art will understandthat certain agents wihave more than one functon ie. a surfactant may alo 30 act as an emulsifier 1.9 Various surfactants, or Mixtures of surftants., can be present in the composition. The surfactants include Mionie, nonionic. canonic. anmhoteric. and zvmtteriOnic surfactants, and mixtures thereof Possible surfactants that may be included in the concentrate of the present invention are all substance of this type which can customarily be employed in agochemical 5 agents. Suitable nononie surfactants melude pol ethylene oxide-polypropylene oxide block copoihmers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethy lene oxide and/or propylene oxide, furthermore poly viny l alco 1 o01 iinv lpvrrolidone, copolymers of polyvinyl alcohol and polyvmyipyrrolidone. and p of methacrvlic acid 0 and nethaerylic acid esters. furthermore alkyl ethoxylates and alkylkuyl ethoxlates which can be optionally phosphated and optionally neutralized with bass (where sorbitol ethoxylates may be mentioned by way of exxyalkyienamie deriuaives are employed. Possible anionic surfactants are all substances of this type which can customarily be employed in agrochernical agttns, Alkali metal aind alkaline earth metal salts of ally isidphonic 15 acids or alkylarylsulphonic acids are preferred. Possible atiuonic surfactants ae all substances of this type which can customarily be employed in agrochemical agents. Quaternary ammoniuun compounds (and mixtures thereof) are preferred Quatermary ammonium compounds include nitrogen-containing surfactants in which the molecular structure indudes a central nitrogen atom joined to four organic groups where at 20 least one organic group is a fatty chain. Examples include nitri-based quaternary compounds (such as monoalky trimethy lmonin salts, dialkltrimnethyiamnoni sits and trialky itrimethy ammonium salts), ester-based compounds (such as meth ldiethanolamine esterquats and triethanolamine esterquats) and ethoxylated quateniary sals (such as monoalkyl quaternary ethoxylates) it has been found by the present inventors that cationic surfaetants 25 improve the adjuvant properties of agricultural acthie compounds, such as gly phosate. Amphoteric or zwitterionic surfattants that are suitable h use in the composition according o the invention include: betaines such as sulphobetaines (sutaines carboxybetaines (regular betaines), phosphobetaines, preferab alkylbetaines or alkyiamidoberaines; akyl amidoaunphoacetatesdlky amlphOacetates, and ami ne oxides, which are optionally poiy 30 alkox, late.

20 The surfactant will be present in the composition of the present invention in an amount effective to improve the emulsifying, dispersing spreading wetting or other sutacc tension related properties of the sprayable formulation of the present invention. In one embodiment, the sufacant is present in the concentrate in an amount of about 20 to about 40% wlw (eyg. about 1 7% "/W). The surfactant may be a mixture of one or more nonionic, one or more ionic, and one or more amphoteric surtactants. In this embodiment, the ionic surfactants are present in an amount of about I to about 5% w/w (e.g. about 3% w/w), the anphoteric surfactants are present in an amount of about 10 to about 30% w/w (e.g. about 20% w/w}, and the lnonnc surfactants are 0 present in an amount of about 10 to about 2.0% w/w (e.g. about 14% w/w) Suitable etulsifiers tor use in the presentnvention nay be any emnusiier that is capable of forming a homogenous wate-rn-ol emulsion when added to the sprayable formulation. Preferred emulsifiers are ethoxylated alcohols and nonylphenols. reaction products of Mcohok or alkvlphenol h with ethylene oxide and/or propylene oide ethoxyated arylalkylphenols, 5 furthermore ethoxylated and propoxylated axylalkylphenols, and suiphated or phosphated aryilkyl ethoxylates or ethoxypropaxylates, where sorbhan derivative, such as polyethylene oxide-sorbitan fatty acid esters and sorbitn fatty acid esters, mvay be mentioned by way of example. Suitable wetting/spreading agents for use in the present invention may be any 20 hydrophilicaily substituted organosi licone surfactant that is capable of lowering the static surface tension of the water in the prayabic fbrmulation. Preferred spreading agents are polysiloxanes belonging to the organosilicone dass of compounds The wetter ay,. for example be selected from: (i) trisiloxane poiyoxyethylene surfactainsof the general formula: 25Si(OTMi hM((C[h-[') where TMSi stands for (CltSiM stands [ r -CLH (E stands fora polyoxyethyeue grouCRp or polyoxypropylene? group -(0CHIp l bCHAcR 1 or a polymer consisting of a combination of polyoxycthylene and polyvxyproylene where n is an integer from 1 to 50, and "21 Feis .H, -iL cxm, -OCH OC(O)Clf 3 or a linear or branched alkyL or aryl group with 1 to 20 carbon atoms; (ii) imethlsilane polyoxyethylene surfactants of the general formula: TMSi(C1It)E OKE/Pt re n is an integer from I to 50, and E/P n R and TMSi have the same nomenclature as above; and (iii) low molecular weight (1500 asmu) polymeric forms based on a substituted siloxane chain of the general formula R -- [Si(RI )O2 -i(RX-R 0 where the X groups can be either the same or different and are either (fP)or -Si(R% 2

O

groups. p is an integer rimm 5 to 30. RI can be either the sane or different and is either near or branched alkxl or arylgroup with up to 20 carbon atoms or is (P4-R 1 group; with the proviso that at least one of theWf groups isan (/P)- group, a equals 0 or an integer from I to 20,and (iP) and R 1 have the same nomenclature as above. 15 Preferably, the wemter is selected frm the letters defined in (i) or i above. in some embodiments, the wener is selected from the waters defined in (I) or (ii) abvce wherein n is an iteger from 10 to 20 and mis an integer from 1 to 10. In other embodiments the wetter is selected from the super letters defined in (iii) above, wherin a equals U or an integer fron I to 10, and p is an integer fon 10 to 20. 20 Suitable letters include for example. cthaxated hepaathitri siloxane, polyethoxylated trisiloxane and ethoxylated polydinethyisiloxane Preferred acidifying agents a pH stabilisers are anionic phosphates (eg polyethylene tridecyl ether phosphatePerably, the acidifying agent or the pH stabilizer is present in the formulaton in an amount of about 01 to about 10% w/w he pH stabilizer maybe present in an 25 amount of about 0.1 to about 5% wvw (eg. about 3% w) The concentrate of the present invention may alo include one or more additives such as antileaching agentstheology modifiers (such as glycoland ethylene giycolf htumectants (esg .22 glycerine or glycol, fluid fertilizes solvents. chelatos(uch as eicacid and EDTA water conditioner (such as inorganic salts 1ike ammonium sulphate, amonium phosphate and urea, and/or acrvlates and n polymers), antiam substances, preservatiesntioxidants, colourants and inert filling materials The additives are all substances which can nitutrily be 5 employed in agroeeical agents for this purpose. Suitable antifoam substances include silicone oils and magnesium tea1ate. Possible preservatives include Prevento® (Lauxess@) and ProxelKt. Suitable antioxidants include butyl hydroxytoluene. Possible colourants include ti1tanium dioxide, carbon black zinc oxide and blue pigments, 0 and Permanent Red FGR, Suitable inert filling materials(which do not fnmetion as thickening agents) include inorganic particles, such as bonatessilicate and oxides and also organic substances, such as urea-formaldehyde condensates Kaolin, rutile, silica highgy disperse silicic acid'), silica gels, natural and synthetic silicates, and tale may be ien tioned by way otexample. As mentioned previously, the oil-based concentrates of the present invention also exhibit improved biological activity (see Example. 5). Without wishing to be bound by any theory or mode of action, the inventar believe that the adjuvancy arises though a number of modes of action, namely: * enhanced x'scoelasticity of the droplets, thereby reducing rebound; 20 * the oil softening the plant cutie, allowing more facie passage ofthe herbiide active through this barrier; * maintenance of the droplet in a liquid state for longer, enhancing the mobility of the active within the droplet allowing greater chance of contact with the kaf surface;and * larger droplets eating a concentration gradient as a driving fore for penetration of the 25 agriculturaly-active compound through the cuticle o athe leaf.

With regard to the -rebound" factor, it has been mentioned above that traditional spray oils and oil concentrates reduce the air entrapment m the large droplets produced by special drit reducing nozzles, thereby increasing the likelihood of rebound from the leaf target, which reduces the efficacy of any agricultural actives contained in the sprayed formulations. Without Swishing to be bound by any theory or mode of action, the inventors believe that the concentrate of the present invention, when added to sprayable formulations, o ercomes this deficiency either through retammg the ability of the anti-drift nobles to entrap air bubbles or by imparting a shock-absorbing property to the spray droplets, which prevems rebound and, accordingly, prevents loss of active from the leaf: The oikbased suspension concentrates used according to the invention may be prepared in such a manner that the components are mixed with One another in the desired ratios The components may be combined in a preferred order such that the components are added one by one and finally the viscosty-modifying agent is added slowly to the mixture while blending/mixing is in progressThe resulting concentrate is a stable fnnation. IThe solid components (in particular the viscositpmodifying agent) are expediently employed in the finely ground state However, itisaso possible to subject the suspension which is formed after combining the components to fine millng or homogenizing through a. grm stator- Preferred suspension Conitrates are those in which the solid particles have a mean parties size of less than 20 gn (e g between I and 10 ptm) 20 The oilh-ased suspension concentrate used accordin. to the invention take the fnn of fornulations that remain stable even following prolonged storage since no deposition of the viseosity modifier is observed hey can be converted into homogeneous sprayable mixtures by dilution with waterhese sprayable mixtures are applied to the desired area by spraying. Accordingly, the present invention also relates to a drift-reducing sprayable liquid 25 omprisin g an aqueous solution, and, dispersed in the aqueous solution, an oilbased liquid concentrate comprising about 0.01 to about 15% w/w of an agent that modifies the viscosity of the spryabl liquid, 56 to about 75% w/w of of selected from vegetabe. paraffI mineral and synthetic oil or mixtures thereof and about I to about 5% w of a dispersing agent in an amount effective to reduce the drift of the sprayabie liquid. 30 The present invention also relates to use of an oi-based liquid concentrate composing; 24 -about 0 M1 to about 15% w/w of an agent that modifies the viscosity of a sprayable liquid containing the oil-based liquid concentrate: 6 to about 754 w/w of oil selected from vegetable, paraffin, mineral and synthetic oil, or mixtures theeof: and 5 -about I toabout 5w/w of a dispersngagent, for the reduAion during spray application, of the dift of the sprayble liquid containing the oil-based liquid concentrate In one embodiment, the sprayable liquid contains at least about 0.000001 to about if % vw/v (e.g, about 0,00005 to about 215% YT) of the oil-based liquid concentate, based on the 1 weight of the sprayable liquid. Preferably, the amount of concetrate inthe sprayale liquid is about 0.25% vv The sprayable quid may also contain additives (as discussed above). In one embodiment, the drift-reducinag sprayable liquid further comprises one or more areulturally-active compounds. By "agricultundiy-active" is meant a compound having art effect on plant growth, 5 whether by kiling undesired organisms or avoiding development thereof, or by directly having an effect on the plant. Examples of suitable agriculturally-active compounds include fungicides, bactericides, insecticides, acaricides nematicides. molluscicides, herbicides, safeners plant growth rgulators plat nutrients. ertlizinig agents, biologicals and repellents. in another embodent, the agiculturally-acdve compound is combined with the oil-based liquid 20 concentrate duing manufacture of a spraybie liquid. Examples of active ingredients include: insecticides, for example carhainates, such as methomylL carbaryL carbofuran, or aldicarb; organ thiophosphates such as EPN, isofenphos. isoxathion, ehlorpyrifos or chlonmephos; organo phosphates such as terbufos monocrotophos, or teracblorinphos; perchlorinated organics such as methoxych Ilor; synthetic pyrethrods suth as 25 fenvalerate, abametin arnd ennamectin henzoate: neonicotinoides uch as thiamethoxam or imnidacloprid; pyreihroids such as lambda-yhalothri, cypermethrin or bifenthrin; and oxadiazines such as indoxacarb, imidachiopryd and fipronil nematicide carbamates, such as oxam'l; herbicides for example triazines such as metribuzin, hexaxinone, or atrazine; suLphonVlUreas such as 2-chloro-N-4-methoxy-6-methyl 1 3,5triazinfyv)arinocarbony- 25 henzenesulphonamide; uracils (pyrimidines) such as lenacl, bromacil, or terbaci ureas suchas linuron, diuron, siduirnw or neburon; acetanilides such as alachlor, or metoiachlor; thiocarhairnates such as benthiocarb (SAR U-RN) or iralt;oxadi.az.-oloynes suchJ as xaiazn phenoxyacee acids such as 2,4-D, dipheni eters such as fluazifbpbutylacfuorfen bifenox oroxyfuorfen; dinitro aniines such as trifluralin; glyci ne phosphonates such as glyphosate salts and esters; dihalobenzonitriles such as bromoxynil, or JOXYnil dipyndi.Iiums such as paraqat; dims such as chiethodiin fops such as fluazifop; fungicide, for example nitrilo oxines such as cvmoxanil urzate imidazoles such as benomyl carbendazim or thiophanate-merhyl:triazoles such as triadimefon sulpheaniides such as captan; dnhio-carbamates such as maneb mancozebi . or thiram; chioronated aronatics such as chirornc dichioo ailnes such as iprodione. strobilurin such as kresonimetyl, trfioxystrobin or azoxystrobn; chlorothalonil; copper salts such as copper oxIchloride sulphur; phenyimidesand derivatis such as metalay or nefenoxam; aphicides, for example carbamates, such as pirimiearb; niticides, for example propynyl sulphites such aspropargie triazapentadienes such as amniraz: chlorinated aromttics 15 such as clorobezilate or tetradifan dinitrophenois such as binapacrylg fbliar fertilizers that provide, for example nitrogen, potassium, phosphoms niemnutrients and other elements necessary for plant growth;and mixtures thereof The sprayable liquid, preferaby the sprayable liquid comprising an agriculturally-active ingredient can be ground sprayed, aerially sprayed or discharged in droplets. This is M) advantageously performed through an appmpriate nozzle, The application rate of the oilbbased concentrates used according tothe invention can be varied within a substantial range. This depends on the agricultray-active substances in question and on their cotent in the concentrates and/or in the sprayable liquids The present invention also relates to a mdhod of making a spravable liquid fornulation 25 for agrochemical application comparing providing an oil-based liquid concentrate comprising about 001 to about 15% w/w of an agent that modifes the viscosity of the sprayable lquid formulation,6 to about 75% wAv of oil selected from vegetable, paraffin, mineral and synthetic oll or mixtures thereof, and about 1 to about 5% w/w of a dispersing agent, in an amount elective to reduce the drift of the spryable 30 liquid formulatin; 26 providing an aqeous soution; and -ombining the oiased liquid concentrate vith the aqueous solution; to form a drift-reducing, sprayable liquid formation. The aqueous solution may comprise one or more agricultural aive pounds 5 Ahematively, the agriculturally-acti e cmnpound(s) may be added to the sprayable liquid formulation afer the combjnining step. The sprayable quid formulations of the present invention vill be prepared in such a manner that The concentrate and the aqueous solution are mixed with one another in the desired ratios. For eIample A 1 Filt the spray tank with water to wo thirds of the required amount and start agitation; 2. Add recommended amount otanti.ddn fornilation and mix the content well; . Add desired agricultural ly active compounds such as herbicides/insecticides and other actives or additives according to correct mixing order and mix thoroughly; and 4, Top up the tank to desired capacity with water. 15 With the aid of the oil-based liquid concentrates used according to the itenden, it is possible to apply agriculturallyactve substances in a particularly advantageous manner to plants and/or their environment. The concentrates of the present invention can be used to treat all plants and plant parts. In the present context, plants are understood as meaning all plants and plant populations, such as 20 desired and undesired wild plants or crop plants Gincluding naturally occurring crop plants). Crop plants can take the form of plants which can be obtained by conventional breeding and optimzation methodsor y ehnologieai and recombinant methods or by mixtures of these methods including the transgenic pi and including the plma varaies capabe Ior not of being protected by Plant Breeders Rights. Plant parts are understood as meaning all aerial and 25 subterranean pars and orgas of the plants such as shoot, leaf flwer and rot. Examples that may be mentioned include leaves, needles stalks, stems, fliers, fruiting bodies,uits and seeds, and also rots, tubers aid rhizomes. The plant part also include harvested material and 27 vegetative and genertive propagation material, for example cuttings tubes rhizomes, slips and seeds. The concentrates of the present invention can be used on cereal plants such as, for example wheat oats, badey spelt, tricale and rye, but also in maize.millet and sorghum ri S sugarcane. soybeans. sunflowers, potatoes. cotton. oilseed rape, canola, tobacco, sugar beet, fodder beet, asparagus hops and fruit phlts omprising pone fruni such as, for exmpie, apples and pears, stone fruit such as, for example peachs nectarines, cherries, plums and apricots. citus fruis such as, for example, oranges, graipefruits, imes, lemons, cumquats. tangerncs and satstmas. nuts such as, for example pistachos almonds, wahuts and pecan nts tropical fruits O such as for example mango, papaya, pineappe dates and bananas and grapes, and vegetables comprising leafy vegetables such as, for epl endivescorn salad, lorence fnnel lettuce cos lette Swiss chard, spinach and chicory, cabbages such as, for example, cauliflower, broccoli Chinese leaves borecole curly ka feathered cabbage. kohlrabi brussels sprouts, red cabbage white cabbage and savoy cabbage, fruit vegetables such a for example athergines; .5 cucumbers. capsicums, table pumpkins, tomatoes courgettes and sweet corn, root vegetables suchas, for example, celeiaearly turnips carrots including yellow cutivas, radish, incuding small radish. beetroot, scorzonera and celery, prdses such as, for example, beans and peas, and bulb vegetAbles such as. for exampIne leeks and table onis The treatment according to the invention of the plants and plant parts with the 20 formulations used according to the: *invention i carried out direct or by acting on their environment, habitat or storage area in accordance with the custom ary treatment methods by spraying on and, in the case of propagation materials, ina particular in the case of seeds, furthermore by applying one or more coats. It wil be understood that the invention disclosed and defined in this specification extends 25 to a alenativ combinations of two or more of the individualfeatures mentioned or evident from the text. All of these different combinations constitute various alternative aspects of the invention. The examples that follow arc intended to illustrate but in no way liinit the present invention, Examples ExampI I Anoibased liquid concentrate was prepared, which contained the ingredients shown in Table I 5 Table 1. Example ingredient list for oil-based liquid concentrate % mass -CAS number Description Purpose 38 4742 Base oil pain4"ic (no agroeemiea) A1Wtill 0 7n891 99 3 Methyl canolue Co native! carrier 1 1876 0 tether sdoxane Non ionic orgranc sihldone wetter!spradair 3 9046-01~ Poyethiene trdy ether phosphate Anmoic surfactant namlsifitei s~er 938953 k col Butyl Ether Non ionlic surfatarit and (alcoh oli polc 1kt ol e thecr)d erigaen E0 b Ik plyme Plusnulsifier and weter) 684 9 Alcohol etho ate [mulsfernvettla agent 2 Blend of amnomium quatemary BIlnded surfadad activator compmind nvCaohydrate polyiner V iSCOSJt modirLr (Hydoxy propyl gar) The concentrate of Table I was prepared as folows: 1. The required amount of paraffinic oil was added to a suitab vessel and the mechanical blender started. ) 2.The vegetable oil was added followed y the nonionie dispersant organo-silionne weetr and anionic sudactant. one after the other, while blending continued. 3. One half of the alcohol emulsifier was hen added, followed by the slow addition of he entire amount of blended emulsifier with continuous mixing.

29( 4. Fhe balance amount ofidlohol enulsitier was added and blended until a cleartansparent mixture formed. 5 Finally the guar was added slowly to the nixture and thoroughly baded until a unifon translucent liquid formed. 5 Example 2 The concentrate of Example 1. was diluted to aspraale dispersion as follows: I Two-thirds of the required amount of water was added to a spray tank and agitation stated 2 The recommended amount of anti-drift formulation was added and the contents mixed well. 0 3 The desired agriculturally active compounds, such as hediiOdes/insecticides, and other actives or additives were added next according to their corret mixing order and miuted thoroughly. 4 The sprytank was topped up to the desired level with water. Example 3 5 The formulation foned in Examplec2 was tested using commonly-used herbicides and a range of hydraulic nozzles to determine the droplet size distribution at a pesticide wind tunnel research facility Fourteen tank mixtures comprising Roundup CT (glyphosate), Roundup DST (double salt, Surpass 300 (2,4-D) and water were sprayed through the following nozzles at designated 20 pressus: TTI-110-02, 3 bar; AITTJ60-110-02, 3 and 5 bar; AJXR- 11002. 2 bar; MD 11002,2 bar: and Agrotop AM 110015, 2 bar, A horizontal air speed of 18 kn/l was applied across the nozzles during the testing while a compressed air cylinder with pressure regulator was used to set the nozzle pressure and monitored by a calibrated pressure gauge placed close to the nozzle. Dropout size was measured using a S ympatec LIELOS VARID Helios laser-diffraction 25 particle-size analyser (Sympatec Gmbi, Germany) with R7 lens (0.3 -- 3500 pin Dynaic Size Range} 150 nm away from the nozzle t ensure full break-up of the spray sheet. 'wo gantries 30 were used to independently position the laser and the nozzle system and allow the emitted spray to be traversed through the laser beam so that the entire spray plume was measured Droplet sizes, droplet size range and % volume of droplets smaller than 150 [tn were measured and the results statisuiatl analysed. Table 2 shows the drifiabbl fines (diameter 1c Stpnt) and Table 3 the droplet size at which 10% of the spray volume is smaller (DVj) and the droplet size at which 50% of the spray volume is smaller (volume median diameter. V&II) produced by each nozzle by the various herbicidc/drift reducing formulation combinations in comparison to a commercially available drft reducing competitor product, LI 700 (350 giL soyal phospholipids and 350 gfl, propionic 0 acid as marketed by Nufrin Australia Ltd), In the tables given in this specification. n.iaiand "nt/a refer to combinations that were not thrilled.

31 Table 2: Percent spray volume in droples smaller than 150 microns. Tank mixture 'IT TTl TT4 AITI AIXR NHD AM RUg 10 1 3 7 25 3 4 RU CT DS 025%1' I 1 4 12 2 3 RU +00S5% 3 0 5 3 6 2 RU C i 12 1 26 12 11 2 2 RJU DS7 16 1 16 $ n/a n a RU DST D025 NY& 1 20 9 14 W/ n/a RU DS1 DS 0.5% 7 6 4 7 n/a nia RU DST l 700 1 1 17 12 8 na n/a RU (I SP300 Io 15 9 27 3 4 RU C - SP 300 DS 025% 5 1 7 9 12 3 RU C1t SP 3004DS A$% 4 1 7 3 11 1 2 RU CT +SP 30- Li 700 n/a n/a n/a n/a n/a 3 RU DS 1 28 1 14 9 15 na aa RU DSrP + DS 65% 10 1 0 7 12 n/a n/a RU )1 A SP + DS 0N% 6 0 6 4 9 a na RU PST SP .1 700 n/a n/a ra 1)a n/a n/a na undyp~~ k7 50 A. 1200 m/L wter; A D ( i = Roundup 19/hual sa/in K 1000 mhIO wa e SP Sw pms (2,4%1) itH sM AN00 m4KL watt- r5- Dri/rehiontkr Wfln~$f$l§/ 25 nd0% vt ct r I r'7ct Nr'7'cM 1-T

A-

<f Cf ' . e ' C C r CC Tt-- -Cr - - $

I-CC'

Example 4 The stability of the concentrate prepTred in Example I wastested using CIPAC standard test recommended in the "Mal aon development and use of FA) aid WHO specifications for pesticides'> The testing comprised acclerated storage stability(CIPAC MT 461 cold storage 5 stabilityCIPAC MT 391) persistent foaming (1PAC MTI 47.2) and container stability. The results of the enulsion and dispersion tes before and after hot torage are given below in Table 4. Table 4: Emulsion Stability after Heat Storage (CIPAC MT 36A1 - 0.25% viv) - -----. .....---------- ... ----- --..................................... Samp Prior to Heat storage After 14 days @4, 54' C CIPAC MT 461) . .. ....-- - - --- - ----

--

initial Enudsifieation/ Uniform Coplete Uniform Complete d Dispersion d - -- ky white m lky white - ------ - ------- ---- ------ ______________________ -- -- - - - Froth n Strike fair fair Emulsion Quality good and stable good and stable ------ ----------------- ~-- -- - - - - ----------------- Emulsion Stability Cream Oi Cream Oil (dispersion stability )(0.25% @i20 min 0 ml 0 ml 0 ml 0 ml @ 2 Hr Oal 0 m (I ml 0 ml @24 Hr 0 ml I mI ml 0 ml Re emulsification ( re Uniform Complte Complete dispersion) @ 24 h -I-. . -- ----- - ---- --... . . . . . . . .-- --- --------------------.. . . . . . . ..-- _ _ _ _ _ _ _ _ _ _ _ _ _ _ Separation/ sediments Cream Oi Cream (O 245hr ml G 1A ml 0 nil 10 The testing showed that the frmulation vas stable under hot and cold storage conditions 34 Example 5 The efficacy of the fTrmulation of Example 2 as an adjuamt was tested with glyphosate and gly phosate plus 2,4-D herbicides against a range of commonly occurring weeds in several replicated small plot tield trials in fallow situations in southern and northern regions of eastern 5 Austraia. The treatments were applied using a 2 metre wide hand held gas operated boom incorporating four of the specified nozzles, At an application speed of 1.75 metres/second and pressures nging from 200 to 500 kPa depending on nozzle type treatments were applied i volumes of from 50 to 65 !/ha. 0 Assessments for weed control were made at 21 or 29 days after treatment (DAT) in the northern trials and 15 DAT in the southern trials by usually the percentage biomass reduction. Control was rated using a Q 100 scale where 0 = no effect 50 = 50% reduction in biomass and 100 100% reduction in biomass. compared to that in theImt. reacted plots, Results are presented as mean percent control SStatistical analyses were conducted using enStat release . 1.11 (C/Windows2008 Lawes Agricultural Trust, Rothamted Experimental Station) A onc-way ANDOVA model was used and included all treatment effects. The data was analysed using analysis of variance and least significant difference (LSD) techniques. Means flanked by a common letter are statistical similar at the 95% level of sigificance. 20 The results of the trials are given below inrables 5 to 9. In summary. the addition of the fornlation of Example 2 at 0.25% v/v to ROUNDUP CT increased the control of all weed species in both the southern and northern trials (Table 5 and 8) readeso ozetpedad despite increasing droplet VMND (Table )+ Sregadles of nozzle type used andcyeJojClNI Tht" Further, the addition ofi the formulation of Example 2 at 0.25% v/v to ROUNDUP CT + 25,4D (Tables 6, 7 and 9) either increased or did not negatively affect control of all weed species in both the southern and northern trials regardless of nozzle type used and despite increasing droplet VMD (fable3 -- - - --. -- ---- m m ...- ----- --- -- - - .) Ia +~ rT C C Ue o Th C C 1 ) -- w - 0 - 4 A ........ a ...... ..... . ~ ~ c .. . ... ................ .....

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Claims (9)

13. An oilbased liquid conentrate according to any one of the preceding claims, wherein the liquid concentrate further comprises one or more additional agents selected from surfactant emukitiers. pH stabsers or acidi in ai reading agents, and mixtures thereof.

14. An oil-based liquid concentrate according to claim 13, wherein the surihetant is 0 present in the formulation in an amount of about 20 to about 40% by weight 15 An oilbased liquid concentrate according to claim 14 wherein the surfactant is present in the formulation in an amount of about 37% by weight. lIt An oilbased liquid concentrate according to any one of claims 13 to 15, wherein the surfactant is a mixture of one or more onic, one or more anphoteric, and one or more non ionie surfactants. I 7 An oil-based liquid concentrate according to claim 16, wherein the ionic suractants are present in an amount of about I to about % /w the aniphteric surfactants are present in an amount of about 10 to about 30% ww and the non-ionic surfactants are present in an a jount of about 10 to about 20% w/w. 20 18, An oibased liquid concentrate according to claim 17, wherein the ionic surfactants are present in an amount of about 3% ww, the amphoteric surfactants are present in an amount of about 20% w/ and the non-ionic surfatamn are present in an amount of about 14% v/w. 19 An oil-based liquid concentrate according to any one of clairns 13 to 18, wherein 25 the emulsifier is present in the concentrate in an amount of about 5 to about 13% w/w

20. An oil-based liquid concentrate according to claim 19 wherein the eusifier is present in the concentrate in an amount of about 10% wW 42

21. An oi-based quid concentrate according to any one of daims lto 20, wherein the pH stabiiser or acidifying age-nt is present in the concentrate in an amount of about 0. to about 10% ww.

22. An oibased liquid concentrate according to claim 21. wherein the pH-1 stabiliser is 5 present in the concentmae in an amount of about 0. to about 5% w/. 23 An oil-basedliid concentrate according to clain 22, wherein the pH-I stabiliser is present in the concentrate in an amount of about 3ww

24. An oil-based liquid concentrate according to any one of claims 13 to 23. wherein the wetting/spreading agent is present in the forutlton in an amount of about 1 to about 10%

25. An oil-based liquid concentrate according to claim 24 wherein the wetting/spreading agent is present in an aImount of about to about 5% w/w

26. An oil-based liquid concentrate according to claim 25. wherein the wetting/spreading agent is present in an arnount of about 2% w/av -5 27, An oilkbased liquid concentrate according to any one of the preceding clais, vweren the QUMhse iquid cnetaedoes not comnpris one or more thceigagent-s. 2 A drift-reducing sprayable liquid comprising an aqueous solution, and, dispersed in the aqueous sohion, an tlbased liquid concentrate comprising about 0.01 to about 15% w/w of an agent that modifies the scosity of the sprayable liquid, 56 to about 75% w/w of oil 20 selected front vegetable, paraffin, mineral and synthetic oil, or mixtures thereof and about I and about 5% w/of a dispersing agent, in an amount effective to reduce the drif o the spravable liquid. 29 A df-reducing sprayable liquid according to clain 28, wherein the oil-based liquid concentrate does not comprise one or more thickening agents 25 30, Ute of an oil-based liquid concentrate comprising; . about 0.01 to about 1% ww of an agent that modifies the viscosyit of a sprayabie liquid containing the oil-based liquid concentrate 4 3 - 56 to about 75% w/w' of oil selected from vegetable, paraffin, mineral or synthetic ol or mixtures thereof; and about I to about 5% /w of a dispersing agent; folr the reduction during spray applica tion of the drift of the sprayable liquid containing 5 the oil-based concentrate. 31 A use according to clain 30, wherein the oil-based liquid concentrate does not comprise one or more thickening agents. 32 A Adrift-reducing sprayable liquid according to claim 28 or 29 or a use according to caim 30 or 31iherein the sprayable liquid contains at least about 0000001 to about 10 %W 0 of the oilbased concentrate, based on the weight of the spravable liquid 33 A drift-reducing sprayable liquid or a use according to claim , wherein the sprayabieleiquid contains about 0.00005 to about 25% vv of the oi-based concentrate.

34. A drift-educing sprayable liquid or a use according to claim 33 wherein the sprayable liquid contains about 0,25% v/v of the oih based concentrate 5 35, A drifi-reducing sprayable liquid according to any one ofclaims 28 29 or 32 to 34, or a use according to any one Of claims 30 to 34, further comprising an agricuiturallfative compound,