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    公开号:AU2006292036A1
    申请号:U2006292036
    申请日:2006-09-15
    公开日:2007-03-22
    发明作者:Aristos Panayi；Chad Richard Ord Sayer；Andrew John Wells
    申请人:Nufarm Australia Ltd；
    IPC主号:A01N25-02
    专利说明:
    WO 2007/030885 PCT/AU2006/001353 1 AGROCHEMICAL EMULSIFIABLE CONCENTRATE 5 This application claims the benefit of Australian Provisional Application 2005905130 (16 September 2005), Australian Provisional Application 2005905131 (16 September 2005) and US Provisional Application No. 60/8786,365 (28 March 2006), the contents of which are incorporated by reference. 10 Field This invention relates to an agricultural chemical composition in the form of an emulsifiable concentrate and to a method of controlling pests using the chemical composition. 15 Background Agricultural chemicals, also known as pesticides, crop protection chemicals or agrochemicals are substances which control unwanted biological species. Herbicides are agricultural chemicals which control weeds, insecticides are 20 agricultural chemicals which control insects and fungicides are agricultural chemicals which control fungi. Most agricultural chemicals are applied by spraying after dilution with a large volume of water. Agricultural chemicals which are insoluble in water but soluble in a low viscosity 25 organic solvent are frequently dissolved in a low viscosity organic solvent and co mixed with surfactants as described in US 2,509,233. The International Union of Pure and Applied Chemistry describes such systems as emulsifiable concentrates, defined as single phase, homogenous liquid pesticide formulations that form an emulsion when added to water. 30 WO 2007/030885 PCT/AU2006/001353 2 Tadros in Surfactants in Agrochemicals, published by Marcel Dekker, 1994 further characterises emulsifiable concentrates as forming a spontaneous emulsion on dilution in water. That is agitation or the application of heat is not required to form the emulsion. 5 Many farmers now wish to reduce the cost of applying agricultural chemicals and fertilizers by substituting a liquid fertilizer as part or all of the water diluent for the agricultural chemical spray. When aqueous solutions of urea and ammonium nitrate (also known as UAN) are used as agricultural spray diluent to partly or 10 wholly replace water, the emusifiable concentrates, which are designed for dilution with water alone fail to emulsify completely. As a consequence the distribution of agricultural chemical through the spray solution is not homgenous and the result of the spray application may be uneven. 15 By way of example we have found that certain herbicides such as the phenoxyalkanoate herbicides and dinitroanilines are incompatible or poorly compatible with fertilizers. This incompatibility may be due to a physical or chemical incompatibility between the compounds and can result in the formation of mixtures and suspensions that clog up spray systems, contribute to disposal 20 costs and lead to poor weed control. As compositions containing a liquid nitrogen fertilizer and herbicides are often not homogeneous mixtures, they often require constant and vigorous agitation in order to ensure adequate mixing of the fertilizer and herbicide prior to use. 25 Phosphate ester surfactants have been recommended for use as a spray tank additive to increase the compatibility of liquid fertilizers with agricultural chemicals. 30 US3,236,626 teaches that higher alkyl aryl sulfonates such as alkali metal, ammonium, magnesium and calcium salts of dodecylbenzenesulfonate are WO 2007/030885 PCT/AU2006/001353 3 entirely unsatisfactory for use as emulsifiers for dilution with liquid fertilizer (column 1 line 51). GB 2 049 427 discloses an emusifiable concentrate comprising at least one 5 biologically-active compound selected from the group consisting of substituted acetanilides, carbamates and anilines; an emulsifier system comprising one or more primaryand/or secondary phosphate esters of ethoxylated mono, di and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols and one or more amines. 10 This patent teaches that separate emulsifiable concentrate formulations are required for dilution by water and dilution by liquid fertilizer (page 4 line 26) Further formulations of the invention do not form a spontaneous emulsion on dilution with liquid fertilizer, indicated by the direction at page 6 line 48 to shake 15 liquid fertilizer and emulsifiable concentrate mixtures vigorously before conducting the stability test. AU742967 discloses formulations including ethoxylated castor oil, ethoxylkated phosphate esters and alkylbenzene sulfonate with lower alkanol esters of fatty 20 acids. The invention provides a composition that forms an emulsion of the lower alkanol ester of fatty acid on dilution. Pesticides may be tank-mixed, but not included in the formulation. US 4,966,728 discloses the use of phosphate ester surfactants as a component 25 of an emulsifiable crop oil, for tank mixing with pesticides. We have now found that certain combinations of components can be used with a range of agricultural chemicals to provide a storage stable composition which spontaneously forms an emulsion with both water and aqueous liquid fertilizers. 30 WO 2007/030885 PCT/AU2006/001353 4 The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in 5 the field relevant to the present invention as it existed before the priority date of this application. We have now found that the use of certain surfactants in the concentrate composition provide a concentrate of good stability and also significantly 10 improves the performance of the concentrate when applied with a fertilizer composition. Summary 15 The invention provides an agrochemical emulsifiable concentrate composition comprising: i). at least one agrochemical active agent preferably in an amount of at least 10% by weight and more preferably from 10 to 80% by weight of the concentrate; 20 ii). a phosphate ester surfactant preferably in an amount of at least 1% by weight and more preferably from 2 to 10% by weight of the concentrate composition; iii). a water immiscible solvent component preferably in an amount of at least 10% and more preferably from 10 to 80% by weight of the 25 concentrate; and iv). an emulsifier composition comprising (a) an alkylarylsulfonate preferably in an amount of at least 1%, more preferably from 2 to 10% by weight of the concentrate and (b) a non-ionic emulsifier preferably in an amount of at least 1% and more preferably from 1 30 to 10% by weight of the concentrate.
    WO 2007/030885 PCT/AU2006/001353 5 In one embodiment the emulsifiable concentrate of the invention comprises from about 30 to about 70% by weight of the composition, of at least one dinitroaniline herbicide or phenoxy alkanoate herbicide. 5 Throughout the specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. 10 Detailed Description In a preferred embodiment of the invention there is provided an agrochemical emulsifiable concentrate comprising: 15 (i) at least one agrochemical active agent, preferably a herbicide and more preferably a dinitroaniline herbicide or phenoxy alkanoate herbicide, in an amount of at least 10% by weight of the concentrate; 20 (ii) a phosphate ester surfactant in an amount of at least 1%, preferably from 1 to 10% and more preferably from 2 to 10% by weight of the concentrate composition; (iii) a water immiscible solvent in an amount of at least 10% and preferably 25 from 10 to 80% of the concentrate; and (iv) an emulsifier composition comprising: (a) an alkylarylsulfonate in an amount of at least 1%, preferably from 1 to 10% and more preferably from 2 to 10% by weight of the concentrate 30 composition; and WO 2007/030885 PCT/AU2006/001353 6 (b) a non-ionic emulsifier in an amount of at least 1% preferably from 1 to 10% by weight of the concentrate composition; In one aspect, the present invention provides a herbicidal composition 5 comprising: (i) from about 30% to about 70% by weight of the composition, of at least one dinitroaniline herbicide; (ii) a phosphate ester surfactant in an amount of at least 1% by weight, preferably from 2% to 10% by weight of the concentrate composition; 10 (iii) a water immiscible solvent component preferably in an amount of at least 10% and preferably from 10% to 80% by weight of the concentrate; (iv) an emulsifier composition comprising (a) an alkylarylsulfonate in an amount of at least 1%, preferably from 1% to 10% and more preferably from 2% to 10% by weight of the concentrate and (b) a non-ionic 15 emulsifier preferably in an amount of at least 1% and more preferably from 1% to 10% by weight of the concentrate. In one embodiment of the invention the emulsifiable concentrate comprises 10 to 80%, and preferably from 20 to 80% of one or more actives, from 2 to 10% 20 phosphate ester surfactant; from 15 to 85% e.g. 30 to 60% of organic solvent; from 1 to 10% alkylarylsulfonate and from 1 to 10% non-ionic emulsifier. Such formulations are particularly preferred for compounds of poor water solubility such as the dinitroanilines and phenoxyalkanoate herbicides. 25 In a further aspect, the present invention also provides a process for preparing a pesticide composition comprising combining from about 30 to about 70% by weight of the composition of active agent component (preferably comprising at least one dinitroaniline herbicide selected from the group consisting of trifluralin, pendimethalin and ethalfluralin); from 2 to 10% by weight if the concentrate 30 composition of a phosphate ester surfactant from 5 to 25% (preferably from 5 to 20%, more preferably from 5 to 17% and still more preferably from 8 to 10% by WO 2007/030885 PCT/AU2006/001353 7 weight) of acetophenone emulsifier component comprising from 1 to 10% by weight of the concentrate composition of alkylarylsulfonate and from 1 to 10% by weight of a non-ionic emulsifier at least 10% by weight an organic solvent of flash point of at least 60.5 C. 5 The ability to store the herbicidal composition for a sustained period of time is beneficial, as it allows the user to purchase a concentrated composition and store the composition until it is desired for use without fear of loss of efficacy over time. As a result, wastage of the composition and costs associated with the disposal of 10 unused herbicide is minimized. Furthermore, as the herbicidal composition of the invention forms stable compositions, any risk associated with the clogging of equipment or incorrect dosage of the herbicide may be avoided. It is preferred that the concentrate composition provide spontaneous 15 emulsification. Spontaneous emulsification particularly preferred because the mixing and spray application equipment used by most farmers does not provide vigorous agitation. 20 Phosphate Ester Examples of suitable phosphate ester surfactants include: (i) alcohol phosphates such as alkyl mono and di-phosphates (eg. N-butyl mono/di-phosphate) and C6 to C10 alkyl phosphate esters; (ii) alcohol ethoxylate phosphates such as C8 to C10 alcohol ethoxylate 25 phosphate esters, tridecyl alcohol ethoxylate phosphate esters, C10 to C15 alcohol ethoxylate phosphate esters, butyl cellosolve phosphate esters, oleyl alcohol ethoxylate phosphate esters; (iii) alkyl phenol ethoxylate phosphates such as nonylphenol ethoxylate phosphate ester and salts thereof and dinonylphenol ethoxylate 30 phosphate ester; WO 2007/030885 PCT/AU2006/001353 8 (iv) aryl phosphate ethoxylate esters such as phenol ethoxylate phosphate esters; and (v) alkyl amine phosphates such as triethylammonium phosphate. 5 The more preferred phosphate ester for use in the invention are C10 to C15 alcohol ethoxylate phosphates and most specifically the phosphonic acid ester with lauryl polyglycol ether. The CAS number of the most preferred ester is 39464-66-9. 10 We have found that by formulating the phenoxyalkanoate concentrate using such a phosphate ester surfactant the concentrate has added stability and is rendered more compatible with fertilizer such as urea-ammonium nitrate on dilution prior to use. 15 Preferably, the surfactant includes C10 to C15 alcohol ethoxylate phosphate esters which we have found are particularly useful in stabilizing the concentrate and also in stabilizing the diluted concentrate when admixed with a fertilizer such as urea ammonium nitrate solution (UAN). 20 A particularly preferred surfactant of this class is the lauryl alcohol phosphated polyglycol ether which is commercially available, for example under the brand
    TERIC
    ® 305 alkyl ester phosphate based surfactant from Huntsman. Without being limited by theory, it is believed that the phosphate group of the 25 phosphate ester surfactant may assist in stabilizing the concentrate and also interact with fertilizer on dilution with a liquid fertilizer to stabilize the herbicidal composition which is applied by spraying or other art recognized application methods. The surfactant may interact with the fertilizer (particularly nitrogenous fertilizers) through ionic or covalent bonds. The interaction enables the herbicidal 30 composition comprising the liquid nitrogenous fertilizer to remain as a stable WO 2007/030885 PCT/AU2006/001353 9 solution or emulsion and minimizes unwanted separation of the components of the composition. Emulsifiers 5 The emulsion concentrate composition of the present invention includes surfactants other than the phosphate ester surfactant. The other surfactants include an emulsifier component which includes an alkylarylsulfonate and a non ionic surfactant. The preferred non-ionic emulsifers are nonionic emulsifiers comprising a polyalkylene oxide derivative. It will be understood that the 10 phosphate ester surfactant while not herein referred to as part of the emulsifier component is involved together with the emulsifier component in providing an emulsion and in particular stabilizing the emulsion even in the presence of liquid fertilizer components. 15 The emulsion concentrate composition preferably does not give rise to crystalline precipitates upon storage for at least 48 hours at 0OC. Nonionic Emulsifier The composition of the invention comprises a nonionic surfactant component. Preferred non-ionic surfactants include the condensation products of alkylene 20 oxide with components forming nonpolar groups such as the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol; the condensation products of ethylene oxide with phenols and alkylphenols such as isooctylphenol, octylphenol and nonylphenol; the condensation products of ethylene oxide with castor oil; the partial esters derived 25 from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate, and their condensation products with ethylene oxide; ethylene oxide/propylene oxide block copolymers; lauryl alcohol polyglycol ether acetal. Examples of nonionic surfactants which may be used alone or in combination in 30 the emulsifier component are listed below, in which EO=ethylene oxide units, such as PO=propylene oxide units and BO=butylene oxide units: WO 2007/030885 PCT/AU2006/001353 10
    C
    1 0
    -C
    24 -alcohols which may be alkoxylated, e.g. with 1-60 alkylene oxide units, preferably 1-60 EO and/or 1-30 PO and/or 1-15 BO in any order. The terminal hydroxyl groups of these compounds can be terminally capped by an alkyl, 5 cycloalkyl or acyl radical having 1-24 carbon atoms. Examples of such compounds are: Genapol ® C, L, O, T, UD, UDD, X products from Clariant, Plurafac ® and Lutensol ® A, AT, ON, TO products from BASF, Marlipal ® 24 and 013 products 10 from Condea, Dehypon ® products from Henkel, Ethylan ® products from Akzo Nobel, such as Ethylan CD 120. Copolymers consisting of EO, PO and/or BO units, such as, for example, block copolymers, such as the Pluronic ® products from BASF and the Synperonic ® 15 products from Uniquema with a molecular weight of from 400 to 108. Alkyleneoxy adducts of C1-C9 alcohols, such as Atlox ® 5000 from Uniquema or Hoe ® -S3510 from Clariant. 20 Fatty acid and triglyceride alkoxylates, such as the Serdox ® NOG products from Condea or alkoxylated plant oils, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, peanut oil, olive oil or rhicinus oil (i.e.castor oil) , in particular rapeseed oil and castor oil, plant oils also being understood as meaning their transesterification 25 products, e.g. alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester, for example the Emulsogen ® products from Clariant, salts of aliphatic, cycloaliphatic and olefinic carboxylic acids and polycarboxylic acids, and alpha sulfo fatty acid esters as available from Henkel. Particularly preferred in this group are castor oil ethoxylates such as TERMUL® 1284 and TERMUL® 1285 30 from Huntsman.
    WO 2007/030885 PCT/AU2006/001353 11 Fatty acid amide alkoxylates, such as the Comperlan ® products from Henkel or the Amam ® products from Rhodia. Alkyleneoxy adducts of alkynediols, such as the Surfynol ® products from Air 5 Products. Sugar derivatives, such as amino and amido sugars from Clariant, glucitols from Clariant, alkyl polyglycosides in the form of the APG ® products from Henkel or such as sorbitan esters in the form of the Span ® or Tween ® products from Uniquema or cyclodextrine esters or ethers from Wacker. 10 Alkyleneoxy adducts based on polyol, such as Polyglycol ® products from Clariant. Interface-active polyglycerides and derivatives thereof from Clariant. Surface-active compounds based on silicone and/or silane, such as the Tegopren ® products from Goldschmidt and the SE ® products from Wacker, and the Bevaloid', Rhodorsil ® and Silcolapse ® products from Rhodia (Dow Corning, 15 Reliance, GE, Bayer). Per- or polyfluorinated surface-active compounds, such as Fluowet ® products from Clariant, the Bayowet ® products from Bayer, the Zonyl ® products from DuPont and products of this type from Daikin and Asahi Glass. 20 Interface-active sulfonamides, e.g. from Bayer. Surface-active polyvinyl compounds, such as modified polyvinylpyrolidone, such as the Luviskol ® products from BASF and the Agrimer ® products from ISP or the derivatized polyvinylacetates, such as the Mowilith ® products from Clariant or the 25 butyrates, such as the Lutonal ® products from BASF, the Vinnapas ® and the Pioloform ® products from Wacker or modified polyvinyl alcohols, such as the Mowiol ® products from Clariant. Surface-active polymers based on maleic anhydride and/or reaction products of 30 maleic anhydride, and maleic anhydride and/or reaction products of copolymers which include maleic anhydride, such as the Agrimer®-VEMA products from ISP.
    WO 2007/030885 PCT/AU2006/001353 12 Surface-active derivatives of montane, polyethylene and polypropylene waxes, such as the Hoechst ® waxes or the Licowet ® products from Clariant. 5 Poly- or perhalogenated surfactants, such as, for example Emulsogen®-1557 from Clariant. Phenols which may be alkoxylated, for example phenyl (C 1 -C4)alkyl ethers or (poly)alkoxylated phenols [=phenol (poly)alkylene glycol ethers], for example 10 having 1 to 50 alkyleneoxy units in the (poly)alkyleneoxy moiety, where the alkylene moiety preferably in each case has 1 to 4 carbon atoms, preferably phenol reacted with 3 to 10 mol of alkylene oxide, (poly)alkylphenols or (poly)alkylphenol alkoxylates [=polyalkylphenol 15 (poly)alkylene glycol ethers], for example with 1 to 12 carbon atoms per alkyl radical and 1 to 150 alkyleneoxy units in the polyalkyleneoxy moiety, preferably tri-n-butylphenol or triisobutylphenol reacted with 1 to 50 mol of ethylene oxide, polyarylphenols or polyarylphenol alkoxylates [=polyarylphenol (poly)alkylene 20 glycol ethers], for example tristyrylphenol polyalkylene glycol ethers with 1 to 150 alkyleneoxy units in the polyalkyleneoxy moiety, preferably tristyrylphenol reacted with 1 to 50 mol of ethylene oxide. Examples of surfactants from the group of aromatic-based surfactants are the surfactants of the abovementioned groups, preferably phenol reacted with 4 to 10 25 mol of ethylene oxide, available commercially, for example, in the form of the Agrisol ® products (Akcros), triisobutylphenol reacted with 4 to 50 mol of ethylene oxide, commercially available, for example, in the form of the Sapogenat ® T products (Clariant), nonylphenol reacted with 4 to 50 mol of ethylene oxide, commercially available, for example, in the form of the Arkopal ® products 30 (Clariant), tristyrylphenol reacted with 4 to 150 mol of ethylene oxide, for example WO 2007/030885 PCT/AU2006/001353 13 from the Soprophor ® series, such as Soprophor" FL, Soprophor ® 3D33, Soprophor ® BSU, Soprophor ® 4D-384, Soprophor ® CY/8 (Rhodia). The non-ionice emulsifier present in the compositions of the invention may 5 comprise one such surfactant or a blend of two or more non-ionic surfactants. Alkylarylsulfonates The composition of the invention comprises an alkylarylsulfonate emulsifier. Alkylarylsulfonates are anionic surfactants and are available in compositions 10 containing suitable counterions which may be optionally substituted ammonium and metal counterions. Examples of alkylarylsulfonates include butylnaphthalenesulfonic acid, the di- and tri-isopropylnaphthalenesulfonic acids, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, the salts of the condensation 15 products of sulfonated naphthalene and naphthalene derivatives with phenol and formaldehyde, and the salts of alkylarylbenzenesulfonic acids such as dodecylbenzenesulfonic acid. Benzenesulfonates, such as alkyl- or arylbenzenesulfonates, e.g. (poly)alkyl- and (poly)arylbenzenesulfonates which are acidic and neutralized with suitable bases, for example having 1 to 12 carbon 20 atoms per alkyl radical or having up to 3 styrene units in the polyaryl radical, preferably (linear) dodecylbenzenesulfonic acid and oil-soluble salts thereof, such as, for example, the calcium salt or the isopropylammonium salt of dodecylbenzenesulfonic acid. It is particularly preferred that the composition of the invention contain a salt of 25 dodeclybenzenesulfonic acid and most preferably calcium dodecylbenzenesulfonate. Solvent The composition of the invention contains a water immiscible solvent. Suitable 30 solvents may be selected from the group consisting of mineral oil fractions such as, for example, kerosene, solvent naphtha, petroleum, coal tar oils and aromatic WO 2007/030885 PCT/AU2006/001353 14 petroleum fractions; aliphatic, cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin, cyclohexane, tetrahydronaphthalene and alkylated aromatics such as alkylated benzenes and naphthalenes; alcohols such as, for example, methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol and 5 propylene glycol; ketones such as, for example, cyclohexanone and isophorone; and strongly polar organic solvents such as, for example, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and sulfolane. In a particularly preferred embodiment alkylated aromatics comprise at least 50% by weight of the solvent, preferably at least 70% and most preferably at least 80 of the solvent component. 10 An example of a particularly preferred hydrocarbon liquid carrier is a long chain alkylbenzene composition such as the C9 - Co10 di- and trialkylbenzenes available from Exxon Mobil as SOLVESSO 150TM Generally, we have found that by using acetophenone as a cosolvent the stability 15 is improved allowing the composition to be formulated with lower flammability solvents so that the compositions can be more safely stored and/and or transported and stored with reduced risk. The use of acetophenone as a cosolvent is particularly preferred for actives of relatively low solubility to achieve a high loading. The composition may, for example, comprise at least 5% by 20 weight acetophenone. Preferably the amount of acetophenone generally does not exceed 25%. Preferably, the herbicidal concentrate composition includes from about 5 to about 20% by weight of the composition of acetophenone. Generally the acetophenone content for obtaining optimal stability will be no more than 15% by weight acetophenone and more preferably no more than 13% by 25 weight acetophenone. Generally the optimum stability is obtained with at least 7% by weight acetophenone and more preferably at least 10% by weight acetophenone. Acetophenone is an aromatic ketone compound which in the preferred 30 embodiment of the invention acts as a cosolvent with the organic solvent. Acetophenone assists in stabilizing the herbicidal composition of the present WO 2007/030885 PCT/AU2006/001353 15 invention by preventing the formation of crystalline precipitates in the composition during storage of the composition. Surprisingly we have found that the effect of acetophenone in enhancing stability is most pronounced when the concentration of the acetophenone is relatively low. A concentration at or approaching from 8 to 5 12 % is particularly preferred in many cases. Thus, for example, we have found that the stability of compositions of about 55% dinitroanilines such as trifluralin in di- and tri-alkyl benzenes as a solvent (where the solvent has a flash point of at least 60.5C) is more stable when 10% acetophenone is p resent rather than 20% acetophenone. The amount of acetophenone which is optimal may vary for 10 different dinitroanilines and mixtures thereof however generally the concentration of acetophenone is in the range of from 5 to 20% by weight and preferably from 8 to 17% by weight. The herbicidal composition of the invention may also include one or more 15 additional surfactants. The surfactant may assist in compatibilizing the components of the herbicidal composition and stabilizing the composition of the present invention through the formation of emulsion or dispersions. The surfactant may be any suitable surfactant, having regard to the solvent, diluent, the extent of dilution required for use of the concentrate and the period of 20 physical stability required following dilution prior to use. The use of additional surfactants may assist in enhancing the stability of the composition. Fertilizer The presence of the surfactant combination (including the phosphate ester 25 surfactant and emulsifier surfactants) and solvent (particularly when in the preferred proportions) in the compositions of the present invention provides compatibility of liquid fertilizer with the one or more active agrochemicals, resulting in a stable concentrate and diluted composition even in the presence of relatively high concentrations of active agents. Even agrochemicals of relatively 30 low solubility such as dinitroaniline herbicides which have previously been found to be incompatible with or poorly compatible with fertilizers such as UAN may be WO 2007/030885 PCT/AU2006/001353 16 used in the emulsifiable concentrate of the invention. While attempts have been made to try and overcome the incompatibility by using additives at the time of dilution and combination with fertilizer, such strategies add complexity and inconvenience to use of concentrates in the field. The ability to use a concentrate 5 composition which at least ameliorates the poor compatibility provides a significant advantage to farmers. The fertilizer may comprise one or more of nitrogen, phosphorous, potassium sulfur and trace elements based fertilizers. The fertilizer is preferably a liquid 10 nitrogenous fertilizer. The liquid nitrogenous fertilizer may be any suitable fertilizer of this type and it would be appreciated by the person skilled in the art that the choice of fertilizer will often be dependent on the type of plant or crop to which the composition of the present invention is to be applied. Preferably, the liquid nitrogenous fertilizer is urea-ammonium nitrate (UAN) or urea-ammonium 15 sulfate (UAS). The liquid nitrogenous fertilizer may be added neat to the composition or it may be diluted with an appropriate solvent prior to its inclusion in the herbicidal composition of the invention. When the liquid nitrogenous fertilizer is diluted, preferably the solvent is water. 20 The amount of liquid nitrogenous fertilizer used in the diluted herbicidal composition may be any concentration that achieves the advantages of the present invention. It would be appreciated by the person skilled in the art that the desired concentration of liquid nitrogenous fertilizer will be dependent upon the type of weed to be controlled and the application rate. 25 In a preferred embodiment, the liquid nitrogen fertilizer is mixed with the concentrate of the invention in an amount of from about 5% to 500% and preferably 20% to 100% by weight of the active agrochemical component of the concentrate composition. 30 WO 2007/030885 PCT/AU2006/001353 17 In a further embodiment the invention provides a method of applying a agrochemical comprising: 5 Providing an emulsifiable concentrate comprising the agrochemical as herein disclosed; combining the emulsifiable concentrate with a liquid nitrogenous fertilizer to form an oil-in-water emulsion having a discontinuous oil phase comprising the water immiscible solvent; 10 applying the oil in water emulsion to the site of use preferably by spray application The emulsifiable concentrate may be combined with the liquid fertilizer with additional water being combined with the concentrate and/ or the fertilizer or 15 alternatively in some cases an emulsion may be formed with the neat concentrate using liquid nitrogenous fertilizer in the form supplied by the manufacturer. Active 20 The agrochemical active agent component may comprise one or more active agents selected from herbicides, insecticides and fungicides. amide herbicides such as allidochlor, beflubutamid, benzadox, benzipram, bromobutide, cafenstrole, CDEA, cyprazole, dimethenamid, dimethenamid-P, diphenamid, epronaz, etnipromid, fentrazamide, flupoxam, 25 fomesafen, halosafen, isocarbamid, isoxaben, napropamide, naptalam, pethoxamid, propyzamide, quinonamid and tebutam; anilide herbicides such as chloranocryl, cisanilide, clomeprop, cypromid, diflufenican, etobenzanid, fenasulam, flufenacet, flufenican, mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor, picolinafen and 30 propanil; WO 2007/030885 PCT/AU2006/001353 18 arylalanine herbicides such as benzoylprop, flamprop and flamprop-M; chloroacetanilide herbicides such as acetochlor, alachlor, butachlor, butenachlor, delachlor, diethatyl, dimethachlor, metazachlor, metolachlor, S metolachlor, pretilachlor, propachlor, propisochlor, prynachlor, terbuchlor, 5 thenylchlor and xylachlor; sulfonanilide herbicides such as benzofluor, cloransulam, diclosulam, florasulam, flumetsulam, metosulam, perfluidone, pyrimisulfan and profluazol; sulfonamide herbicides such as asulam, carbasulam, fenasulam, oryzalin, penoxsulam and pyroxsulam, see also sulfonylurea herbicides; 10 thioamide herbicides such as bencarbazone and chlorthiamid; antibiotic herbicides such as bilanafos; aromatic acid herbicides benzoic acid herbicides such as chloramben, dicamba, 2,3,6-TBA and tricamba; 15 pyrimidinyloxybenzoic acid herbicides such as bispyribac and pyriminobac; pyrimidinylthiobenzoic acid herbicides such as pyrithiobac; phthalic acid herbicides such as chlorthal; picolinic acid herbicides such as aminopyralid, clopyralid and picloram; 20 quinolinecarboxylic acid herbicides such as quinclorac and quinmerac; arsenical herbicides such as cacodylic acid, CMA, DSMA, hexaflurate, MAA, MAMA, MSMA, potassium arsenite and sodium arsenite; WO 2007/030885 PCT/AU2006/001353 19 benzoylcyclohexanedione herbicides such as mesotrione, sulcotrione, tefuryltrione and tembotrione; benzofuranyl alkylsulfonate herbicides such as benfuresate and ethofumesate; 5 carbamate herbicides such as asulam, carboxazole, chlorprocarb, dichlormate, fenasulam, karbutilate and terbucarb; carbanilate herbicides such as barban, BCPC, carbasulam, carbetamide, CEPC, chlorbufam, chlorpropham, CPPC, desmedipham, phenisopham, phenmedipham, phenmedipham-ethyl, propham and swep; 10 cyclohexene oxime herbicides such as alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, profoxydim, sethoxydim, tepraloxydim and tralkoxydim; cyclopropylisoxazole herbicides such as isoxachlortole and isoxaflutole; dicarboximide herbicides such as benzfendizone, cinidon-ethyl, 15 flumezin, flumiclorac, flumioxazin, and flumipropyn; dinitrophenol herbicides such as dinofenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinofen and medinoterb; diphenyl ether herbicides such as ethoxyfen; nitrophenyl ether herbicides such as acifluorfen, aclonifen, bifenox, 20 chlomethoxyfen, chlornitrofen, etnipromid, fluorodifen, fluoroglycofen, fluoronitrofen, fomesafen, furyloxyfen, halosafen, lactofen, nitrofen, nitrofluorfen and oxyfluorfen; dithiocarbamate herbicides such as dazomet and metam; WO 2007/030885 PCT/AU2006/001353 20 halogenated aliphatic herbicides such as alorac, chloropon, dalapon, flupropanate, hexachloroacetone, iodomethane, methyl bromide, monochloroacetic acid, SMA and TCA; imidazolinone herbicides such as imazamethabenz, imazamox, 5 imazapic, imazapyr, imazaquin and imazethapyr; inorganic herbicides such as ammonium sulfamate, borax, calcium, chlorate, copper sulfate, ferrous sulfate, potassium azide, potassium, yanate, sodium azide, sodium chlorate and sulfuric acid; nitrile herbicides such as bromobonil, bromoxynil, chloroxynilm, 10 iodobonil, ioxynil and pyraclonil; organophosphorus herbicides such as amiprofos-methyl, anilofos, bensulide, bilanafos, butamifos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate, glyphosate, and piperophos; oxadiazolone herbicides such as dimefuron, methazole, oxadiargyl and 15 oxadiazon; phenoxy herbicides such as bromofenoxim, clomeprop, 2,4-DEB, 2,4 DEP, difenopenten, disul, erbon, etnipromid, fenteracol and trifopsime; phenoxyacetic herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA, MCPA-thioethyl and 2,4,5-T; 20 phenoxybutyric herbicides such as 4-CPB, 2,4-DB, 3,4-DB, MCPB and 2,4,5-TB; phenoxypropionic herbicides such as cloprop, 4-CPP, dichlorprop, dichlorprop-P, 3,4-DP, fenoprop, mecoprop and mecoprop-P; WO 2007/030885 PCT/AU2006/001353 21 aryloxyphenoxypropionic herbicides such as chlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, fenoxaprop-P, fenthiaprop, fluazifop, fluazifop-P, haloxyfop, haloxyfop-P, isoxapyrifop, metamifop, propaquizafop, quizalofop, quizalofop-P and trifop; 5 phenylenediamine herbicides such as dinitramine, and prodiamine; phenyl pyrazolyl ketone herbicides such as benzofenap, pyrasulfotole, pyrazolynate, pyrazoxyfen and topramezone; pyrazolylphenyl herbicides such as fluazolate, nipyraclofen and pyraflufen; 10 pyridazine herbicides such as credazine, pyridafol and pyridate; pyridazinone herbicides such as brompyrazon, chloridazon, dimidazon, flufenpyr, metflurazon, norflurazon, oxapyrazon and pydanon; pyridine herbicides such as aminopyralid, cliodinate, clopyralid, dithiopyr, fluroxypyr, haloxydine, picloram, picolinafen, pyriclor, thiazopyr and triclopyr; 15 pyrimidinediamine herbicides such as iprymidam and tioclorim; quaternary ammonium herbicides such as cyperquat, diethamquat, difenzoquat, diquat, morfamquat and paraquat; thiocarbamate herbicides such as butylate, cycloate, di-allate, EPTC, esprocarb, ethiolate, isopolinate, methiobencarb, molinate, orbencarb, pebulate, 20 prosulfocarb, pyributicarb, sulfallate, thiobencarb, tiocarbazil, tri-allate and vernolate; thiocarbonate herbicides such as dimexano, EXD, proxan and eptam (EPTC); thiourea herbicides such as methiuron; WO 2007/030885 PCT/AU2006/001353 22 triazine herbicides such as dipropetryn; triaziflam and trihydroxytriazine; chlorotriazine herbicides such as atrazine; chlorazine, cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine, propazine, sebuthylazine, simazine, terbuthylazine and trietazine; 5 methoxytriazine herbicides such as atraton, methometon, prometon, secbumeton, simeton and terbumeton; methylthiotriazine herbicides such as ametryn, aziprotryne, cyanatryn, desmetryn, dimethametryn, methoprotryne, prometryn, simetryn and terbutryn; triazinone herbicides such as ametridione, amibuzin, hexazinone, 10 isomethiozin, metamitron and metribuzin; triazole herbicides such as amitrole, cafenstrole, epronaz and flupoxam; triazolone herbicides such as amicarbazone, bencarbazone, carfentrazone, flucarbazone, propoxycarbazone and sulfentrazone; triazolopyrimidine herbicides such as cloransulam, diclosulam, 15 florasulam, flumetsulam, metosulam and penoxsulam; uracil herbicides such as butafenacil, bromacil, flupropacil, isocil, lenacil and terbacil; urea herbicides such as benzthiazuron, cumyluron, cycluron, dichloralurea, diflufenzopyr, isonoruron, isouron, methabenzthiazuron, 20 monisouron and noruron; phenylurea herbicides such as anisuron, buturon, chlorbromuron, chloreturon, chlorotoluron, chloroxuron, daimuron, difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluothiuron, isoproturon, linuron, methiuron, methyldymron, metobenzuron, metobromuron, metoxuron, monolinuron, WO 2007/030885 PCT/AU2006/001353 23 monuron, neburon, parafluron, phenobenzuron, siduron, tetrafluron and thidiazuron; sulfonylurea herbicides including: pyrimidinylsulfonylurea herbicides such as amidosulfuron; 5 azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, mesosulfuron, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron and trifloxysulfuron; 10 triazinylsulfonylurea herbicides such as chlorsulfuron, cinosulfuron, ethametsulfuron, iodosulfuron, metsulfuron, prosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuron and tritosulfuron; and thiadiazolylurea herbicides such as buthiuron, ethidimuron, tebuthiuron, thiazafluron and thidiazuron; and 15 unclassified herbicides such as KIH-485, acrolein, allyl alcohol, azafenidin, benazolin, bentazone, benzobicyclon, buthidazole, calcium cyanamide, cambendichlor, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, cinmethylin, clomazone, CPMF, cresol, ortho-dichlorobenzene, dimepiperate endothal, fluoromidine, fluridone, flurochloridone, flurtamone, fluthiacet, 20 indanofan, methyl isothiocyanate, OCH, oxaziclomefone, pentachlorophenol, pentoxazone, phenylmercury acetate, pinoxaden, prosulfalin, pyribenzoxim, pyriftalid, quinoclamine, rhodethanil, sulglycapin, thidiazimin, tridiphane, trimeturon, tripropindan and tritac. 25 Examples of insecticides which may be used in composites of the invention include WO 2007/030885 PCT/AU2006/001353 24 antibiotic insecticides, avermectin insecticides, milbemycin insecticides, spinosyn insecticides, carbamate insecticides, benzofuranyl methylcarbamate insecticides, dimethylcarbamate insecticides, oxime carbamate insecticides, phenyl methylcarbamate insecticides, diamide insecticides, desiccant insecticides, 5 dinitrophenol insecticides, fluorine insecticides, formamidine insecticides, insect growth regulators, chitin synthesis inhibitors, juvenile hormone mimics, juvenile hormones, moulting hormone agonists, moulting hormones, moulting inhibitors, precocenes, unclassified insect growth regulators, nereistoxin analogue insecticides, nicotinoid insecticides, nitroguanidine insecticides, nitromethylene 10 insecticides, pyridylmethylamine insecticides, organochlorine insecticides cyclodiene insecticides, organophosphorus insecticides, heterocyclic organothiophosphate insecticides, phenyl organothiophosphate insecticides, oxadiazine insecticides, oxadiazolone insecticides, phthalimide insecticides, pyrazole insecticides, pyrethroid insecticides, pyrimidinamine insecticides 15 pyrrole insecticides, tetramic acid insecticides, tetronic acid insecticides, thiourea insecticides, urea insecticides, and unclassified insecticides such as closantel copper naphthenate, crotamiton EXD fenazaflor, fenoxacrim, hydramethylnon, isoprothiolane, malonoben, metaflumizone, nifluridide, pyridaben, pyridalyl pyrifluquinazon, rafoxanide, triarathene and triazamate. 20 Examples of fungicides which may be used in compositions of the invention include aliphatic nitrogen fungicides, amide fungicides, acylamino acid fungicides, anilide fungicides, benzamide fungicides, furamide fungicides, phenylsulfamide fungicides, sulfonamide fungicides, valinamide fungicides, 25 antibiotic fungicides, aromatic fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzothiazole fungicides, bridged diphenyl fungicides, conazole fungicides, copper fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, imidazole fungicides, morpholine fungicides, organophosphorus fungicides, organotin fungicides, oxathiin fungicides, oxazole 30 fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quinoline fungicides, quinone WO 2007/030885 PCT/AU2006/001353 25 fungicides, quinoxaline fungicides, thiazole fungicides, thiocarbamate fungicides thiophene fungicides, triazine fungicides, triazole fungicides, urea fungicides and unclassified fungicides such asacibenzolar, acypetacsk, allyl alcohol, benzalkonium chloride, benzamacril, bethoxazin, carvone, chloropicrin, DBCP, 5 dehydroacetic acid, diclomezine, diethyl pyrocarbonate, fenaminosulf, fenitropan fenpropidin, formaldehyde, furfural, hexachlorobutadiene, iodomethane isoprothiolane, methyl bromide, methyl isothiocyanate, metrafenone, nitrostyrene, nitrothal-isopropyl, OCH, 2-phenylphenol, phthalide, piperalin, probenazole, proquinazid, pyroquilon, sodium orthophenylphenoxide, spiroxamine, sultropen, 10 thicyofen, tricyclazole and zinc naphthenate. Dinitroanilines (more specifically 2,6-dinitroanilines) are a group of herbicides used to control many grasses and broadleaf weeds. The dinitroanilines are most 15 commonly used as pre-emergent herbicides and are incorporated in soil to control weeds in many important crops such as soya been, cotton, tobacco, tomatoes, cereals, canola, pulses and legume crops. Dinitroanilines are of general formula I 20 Y NO2 X O NR 1
    R
    2
    NO
    2 Wherein X is selected from lower alkyl, halogenated lower alkyl, lower alkyl sulfonyl and 25 amino sulfonyl; Y is hydrogen or lower alkyl
    R
    1 is hydrogen or lower alkyl: and
    R
    2 is lower alkyl, lower alkenyl or halogenated lower alkyl.
    WO 2007/030885 PCT/AU2006/001353 26 The lower alkyl/alkenyl fragments are typically C, to C4alkyl/C2 to 04 alkenyl. 5 The preferred phenoxyalkanoic alkanoate herbicides for use in the composition of the invention are of formula I X' X
    R
    1 0 lI II Cl O(CH)nC-R 2 I X x Wherein 10 X is selected from hydrogen, halogen (preferably chloro) and methyl, preferably from hydrogen and chloro and most preferably is hydrogen;
    X
    1 is selected from the group of hydrogen, halogen (preferably chloro) and methyl, preferably chloro and methyl and most preferably chloro;
    R
    1 is selected from hydrogen and methyl and preferably is hydrogen; 15 R 2 is selected from OR 3 and NR 4
    R
    5 wherein R 3 is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, alkyl (preferably C, to C10 alkyl and more preferably C3 to C8 alkyl), hydroxyalkyl (preferably C, to C10 and more preferably C3 to C8 hydroxyalkyl), alkoxyalkyl (preferably C, to C10 alkoxy(C to C10 alkyl) and more 20 preferably C, to C 8 alkoxy(C 2 to C8 alkyl)), hydroxyalkoxyalkyl (preferably hydroxy C2 to C 4 alkoxy substituted C2 to C8alkyl) and NR 4
    R
    5
    R
    6 ; and wherein R 4 , R 5 and R 6 are independently selected from hydrogen, C 1 to C6 alkyl and C to C6hydroxyalkyl; and n is from 1 to 3. 25 The preferred phenoxy alkanoates are compounds wherein R 2 is OR 3 where R 3 is selected from hydrogen, alkali metal, C3 to C8alkyl, hydroxy(C 2 to C 6 alkyl), C, to WO 2007/030885 PCT/AU2006/001353 27 C4 alkoxy(C 2 to 06 alkyl), hydroxy(C 2 to 04 alkoxy)C 2 to 06 alkyl and the group
    NR
    4 Rs 5
    R
    6 wherein R 4 and R 5 are independently hydrogen or C, to C8 alkyl and C2 to C8hydroxyalkyl and R 6 is hydrogen. 5 Specific examples of the herbicides used in the compositions of the inventions include: 2,4-D (2,4-dichlorophenoxyacetic acid), 2,4-DB 2-(2,4-dichlorophenoxy)butyric acid, domeprop 2-(2,4 dichloro-m-tolyloxy)propionanilide, 10 dichlorprop (RS)-2-(2,4-dichlorophenoxy)propionic acid, dichlorprop-P (R)-2-(2,4-dichlorophenoxy)propionic acid, fenoprop (+)-2-(2,4,5 trichlorophenoxy)propionic acid, MCPA 4-chloro-o-tolyloxyacetic acid, MCPB 4-(4-chloro-0-tolyloxy)butyric acid, 15 Mecoprop (RS)-2-(4-chloro-o-tolyloxy)propionic acid, Mecoprop-P (R)-2-(4-chloro-o-tolyloxy)butyric acid, papropamide (RS)-N,N-diethyl-2-(1 -naphthoxy)propionamide, triclorpyr 3,5,6-trichloro-2-pyridyloxyacetic acid, 20 and where the compound listed is the acid the compound may be in the corresponding ester formed with an alcohol of formula R 3 OH, salt forms particularly alkali metal, ammonium and salts of formula NR 4
    R
    5
    R
    6 wherein R 4 ,
    R
    5 are independently selected from hydrogen and C1 to C4 alkyl, C2 to 06 hydroxyalkyl and R 6 is hydrogen. 25 The more preferred herbicides are 2,4-D, MCPA, dichlorprop, dichlorprop-P, mecoprop, mecoprop-P, 2,4-DB, MCPB and the esters thereof. Phenoxyalkanoate herbicides have previously been considered to have poor 30 compatibility with fertilizers such as UAN. While attempts have been made to try and overcome the incompatibility by using additives at the time of dilution and WO 2007/030885 PCT/AU2006/001353 28 combination with fertilizer, such strategies add complexity and inconvenience to use of concentrates in the field. The ability to use a concentrate composition which at least ameliorates the poor compatibility provides a significant advantage to farmers. 5 In a further aspect, the present invention provides a method of controlling weeds comprising applying a herbicidally effective amount of a herbicidal composition or a ready to use herbicidal composition as described herein to an area of land comprising weeds and/or in which pre-emergent control is desired. 10 Liquid compositions of the invention may be applied by spraying, atomizing, watering, introduction into the irrigation water, or any other suitable means for broadcasting or spreading the liquid. The rate of application of the compositions of the invention will depend on a 15 number of factors including, for example, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use, whether the compound is to be applied for pre-emergent or post-emergent control and whether for foliage or root uptake. As a general guide, however, an application rate of from 0.01 to 20 kilograms of compound of formula I per 20 hectare (based on phenoxy acid equivalent) is suitable while from 0.1 to 10.0 kilograms of the may be preferred. The present invention is described with reference to the following examples. It is to be understood that the examples are illustrative of and not limiting to the 25 invention described herein.
    WO 2007/030885 PCT/AU2006/001353 29 Examples The present invention is described with reference to the following examples. It is 5 to be understood that the examples are illustrative of and not limiting to the invention described herein. Example 1: Two formulations having 480 and 500 g/L of trifluralin were prepared. For each 10 formulation, ca. 6 % of TERIC ® 305 (a phosphorylated alcohol ethoxylate in SOLVESSO 150TM was added. The trifluralin raw material used contains two surfactants - KEMMAT HF60 and TERMUL ® 1284. KEMMAT HF60 is a solution of calcium dodecylbenzenesulfonate in 2-ethylhexanol supplied in Australia by APS, a division of Nuplex Industries (Aust) Pty Ltd. Trifluralin formulations 15 containing 3% KEMMAT HF60 and 2 % TERMUL ® 1284 provided the highest composition emulsion stability. Water emulsion stability studies with tap, water prepared to CIPAC Standard C and 3 WHO water (prepared as CIPAC Standard C, with total hardness 1000 ppm as calcium) showed acceptable results, however cold storage stability studies showed significant crystal formation (8 and 20 16 % for 480 and 500 g/L respectively). Storage stability trials were conducted by placing a sample of the composition in a refrigerator at 01C for 48 hours. After 48 hours the sample was seeded with trifluralin crystals prepared from the formulation matrix and placed back in the refrigerator for another 48 hours. 25 Example 2: Herbicidal Composition - 10 % Acetophenone Two (480 and 500 g/L trifluralin) formulations were then prepared as in Example 1 but containing 20 % (w/v) of acetophenone in place of a portion of the SOLVESSO 150TM in order to improve solubility of the active ingredient trifluralin. The emulsion stability in water was satisfactory. Cold storage stability showed no 30 crystallisation in the case of 480 g/L formulation and 5.5 % crystal formation for the 500 g/ L trifluralin formulation. In order to minimise the cost of the proposed WO 2007/030885 PCT/AU2006/001353 30 formulation as well as to reduce the amount of modifications to the existing trifluralin formulation, a reduction in the content of acetophenone was attempted whereby 10 % w/v of the acetophenone was utilised. The new formulation is detailed in Table 1. 5 Table 1: Trifluralin formulations containing TERIC ® 305) composition Ingredient Composition I Composition II Content, % (w/v) Content, % (w/w) Trifluralin 44.8 45.0 (equivalent 480 g/IL) (equivalent to 500 g/L) KEMMAT HF60 2.8 2.8 TERMUL 1284 1.9 1.8 TERICO 305 5.6 5.5 Acetophenone 9.3 9.2 SOLVESSO 150TM To the volume required To the volume required Emulsion stability tests on both 480 and 500 g/L formulations showed an acceptable stability in Melbourne tap (20ppm hardness), CIPAC standard C 10 (500ppm hardness) and 3 WHO waters (1000 ppm hardness) at 300C. These results show that the formulations containing 480 g/L and 500g/L trifluralin provides a reasonably stable emulsion in tap, CIPAC STD C and 3WHO waters 15 Cold storage stability studies showed no visible crystallisation following standing at 00C for 48 hours. Only upon seeding the samples did crystal formation occur (5.4 and 8.0 % for 480 and 500 g/L formulation respectively). As a comparison, crystal formation in the commercially available TriflurXTM composition (an emusifiable concentrate formulation containing 480 g/L trifluralin, supplied by 20 Nufarm Australia Limited) typically comprises 5 % after seeding. As a result, it is determined that the 480 g/L and 500g/L trifluralin compositions of the invention have a satisfactory cold stability. Example 3: Compatibility Studies WO 2007/030885 PCT/AU2006/001353 31 Compatibility studies were performed on the 500 g/L formulation of Table 1, which is herein denoted as Composition II. An amount of various herbicidal formulation(s) appropriate for the given 5 application rate was added to either CIPAC standard C water (for comparative assessment) or to a neat aliquot of the commercially available urea-ammonium nitrate liquid fertilizer, Flexi-N
    ®
    , to make up to a total for 100 ml in a crow receiver. The crow receiver was stoppered and inverted 10 times. The type and degree of separation / precipitation at various times was then recorded over 2 10 hours at ambient temperature. If any phase separation had occurred after 2 hours, the crow receiver was then re-inverted ten times. The amount of phase separation at 30 seconds after re-inversion was then recorded. The results obtained when the composition are added to undiluted Flexi-N® " shown in Table 3, while the comparative results that are obtained when the composition is added 15 to CIPAC standard C water is shown in Table 2. Results Table 2: Compatibility in CIPAC Standard C water Formulation(s) Observation Comments Composition II (5ml) Compatible with Forms an emulsion which CIPAC std C water (95 ml) agitation showed 11 ml of cream formation after 2 h. Re emulsifies upon re-inversion Roundup PowerMAX7 (10 ml) Compatible Forms clear solution CIPAC std C water (90 ml) Composition II (5 ml) Compatible with Forms an emulsion which shows Roundup PowerMAX (10 ml) agitation 7 ml of cream formation after 2 h. Re-emulsifies after re CIPAC std C water (85 ml) inversion Surpass 300 (6 ml) Compatible Forms clear solution CIPAC std C water (94 ml) Composition II (5 ml) Compatible with Forms an emulsion which Surpass 300 (6 ml) agitation shows 6 ml of cream formation after 2 h. Re CIPAC std C water (89 ml) emulsifies after re-inversion Diuron 900 (3 g) Compatible with Forms an emulsion which shows CIPAC STD C water to 100 ml constant agitation 3 ml of solid after 2 h. Re- WO 2007/030885 PCT/AU2006/001353 32 emulsifies after 15 re-inversions. Composition II (5 ml) Compatible with Forms an emulsion which shows Diuron 900 (3 g) constant agitation 2 ml of solid and 6 ml after 2 h. Solid did not re-suspend even CIPAC STD C water to 100 ml Solid did not re-suspend even after 20 inversions. Roundup PowerMAX' is a registered trademark of Monsanto for a formulation containing 540 g/L glyphosate acid equivalent, present as the potassium salt, distributed in Australia by Nufarm Australia Limited. Flexi-N' is a registered trade mark of CSBP for a urea ammonium nitrate 5 fertilizer. Diuron 900 DF is a dispersible granule formulation containing 900 g/kg diuron, supplied by Nufarm Australia Limited. Table 3: Compatibility in undiluted Flexi-N® @ Formulation(s) Observation Comments Composition II (5ml) Compatible Forms an emulsion which showed no Flexi-N@ (95 ml) with agitation cream formation after 2 h. Composition II Compatible Forms an emulsion which shows (5 ml) with Agitation separation after 2 h into 7 ml of brown cream (top) and green suspension Roundup PowerMAX® containing solid. Re-emulsifies after re (10 ml) inversion. Flexi-N® (85 ml) Surpass ® 300 (6 ml) Incompatible Immediate solid formation. Severe solid Flexi-N(94 ml) formation after 2 h. Re-inversion did not improve the outcome. Composition II (5 ml) Incompatible Good emulsion forms initially. Surpass 300 (6 ml) Separation with cream and solid formation occurs after 2 h. Oil re Flexi-N® (89 ml) emulsifies upon re-inversion but the crystalline solid remains. 10 The above compatibility tests show somewhat mixed compatibility results when the various herbicide compositions are mixed with undiluted Flexi-N® ®. As a result, compatibility tests were then conducted with diluted Flexi-N® ® and with CIPAC standard C water. In this study, 20 ml of CIPAC standard C water WO 2007/030885 PCT/AU2006/001353 33 was used in each trial to which the formulation(s) was/ were added, following by making up to 100 ml with Flexi-N® . The results are summarised in Table 4. Table 4: Compatibility in Standard Flex-N containing 20 % (v/v) standard 5 CIPAC STD C water Formulation(s) Observation Comments Composition II (5ml) Compatible Forms an emulsion which CIPAC std C water (20 ml) with agitation showed 1 ml of cream formation after 2 h. Re-emulsifies upon re Flexi-N® ® (75 ml) inversion. Roundup PowerMAX8 (10 ml) Compatible Forms a clear solution CIPAC std C water (20 ml) Flexi-N® (70 ml) Composition II (5 ml) Compatible Forms an emulsion which shows Roundup PowerMAX® (10 ml) with agitation separation with formation of 7 ml of cream. Re-emulsifies upon CIPAC std C water (20 ml) re-inversion. Flexi-N® (65 ml) Composition II (5 ml) Compatible Forms an emulsion initially when with constant Diuron is suspended in water Diuron 900 (3 g) agitation first. 2 ml of cream and 1 ml of CIPAC std C water (20 ml) solid form on top and bottom Flexi-N® to 100 ml respectively. Cream re emulsifies upon re-inversion but solid needed very vigorous shaking to be re-suspended. From this study, it is determined that Composition II is compatible or compatible with agitation when mixed with Roundup PowerMAX', Surpass ® 300 and Diuron 10 900 DF in CIPAC standard water C at the rates indicated herein. In addition, Composition II can be emulsified with agitation in undiluted Flexi-N' and is also compatible with Roundup PowerMAX ® (at the rate specified) in undiluted Flexi-N ® . Composition II, is incompatible with either Surpass ® 300 or Diuron 900 DF in undiluted Flexi-N
    ®
    . 15 WO 2007/030885 PCT/AU2006/001353 34 When mixed with diluted Flexi-N ® having 20% standard CIPAC standard C water, Composition II is compatible in with Roundup PowerMAX®,,and Diuron 900 DF (with constant agitation), but is incompatible with Surpass ® 300. 5 Example 4: Compatibility Study of 3-way Mixes Compatibility studies were performed on Composition II. in combination with various herbicidal formulation(s) in dilute Flexi-N' containing 20% CIPAC standard C water. The results are shown in Table 5. Table 5: Compatibility of 3-way mixes in Standard Flex-N® containing 20 % (v/v 10 CIPAC) standard C water Formulation(s) Observation Comments Composition II. (5ml) Forms an emulsion but some Roundup PowerMAXG, (5ml) separation into 3 ml of oil (top) and 13 ml of solid (bottom). Surpass 300 (5 ml) Some crystals still present upon CIPAC std C water (20 ml) re-inversion. Flexi-N® (65 ml) Composition II. (5ml) Compatible with Forms emulsion initially which Roundup PowerMAXG, (5 ml) agitation separates into 1.5 ml of solid (bottom) and 4 ml oil (top). Re Diuron 900 DF (3 g) emulsifies upon inversion. CIPAC std C water (20 ml) Flexi-N® to 100 ml Three-way mixing experiments show that Composition II. is compatible with agitation when prepared in Flexi-N' diluted with standard water C (20 %), with Roundup PowerMAX
    ®
    , and Diuron 900 DF. 15 Example 5 An emulsifiable concentrate product containing 650g/L 2,4-D (present as the 2 ethylhexyl ester) was prepared: prepared based on the following formulation details shown in Table 6: WO 2007/030885 PCT/AU2006/001353 35 Table 6: Details of Composition Ill Constituent (common name) Concentration [g/L) 2,4-D 2-Ethylhexyl ester (96.0)% 1020.0 Sufficient to give 650 g/L 2,4-D) KEMMAT HF 60 40.0 TERMUL7 1285 10.0 TERMUL7 12854 40.0 TERICO 305 30.0 5 The emulsifier components were added with mixing to the active in the order listed and mixing was continued for about 20 minutes thereafter. The formulation was tested chemically and physically and then some of the formulation was divided into a 1-L high density polyethylene container and a 1-L 10 unlined tin-plated container and stored at 540C for two weeks. At the end of the two-week period, the sample was tested for chemical, physical and emulsion characteristics. The composition was found to be stable when stored at 00C, for 7 days or 540C for 14 days in high density polyethylene and tin 15 plated containers. Example 6 A composition of the invention in accordance with Composition Ill was mixed with
    FLEXI-N
    ® liquid fertilizer at a dilution of 5/95. The herbicidal concentrate formed 20 an emulsion quickly on mixing which remained stable for up to 24 hours. Any evidence of separation after 24 hours or more from initial emulsion formation can generally be rectified by mixing.
    WO 2007/030885 PCT/AU2006/001353 36
    FLEXI-N
    ® is a solution fertilizer containing urea ammonium nitrate available from CSBP Limited. Example 7 5 Composition VI is a fungicide, propiconazole 500 g/L emulsifiable concentrate product which is compatible when mixed/diluted with Flexi-N'. PROCEDURE Various formulations were prepared (refer to Table 7) and then the formulations 10 were evaluated by diluting/mixing them with Flexi-N® ® to evaluate which formulation is compatible with Flexi-N® ®. Table 7: Composition details for fungicide emusifiable concentrate Material Composition Composition Compostion Composition IV V VI VII (g) (g) (g) (g) Propiconazole technical 526.3 526.3 526.3 526.3 (95%) KEMMAT HF60 55.0 55.0 55.0 55.0 TERMULO 1284 20.0 20.0 20.0 20.0 TERMULO 1285 25.0 25.0 25.0 25.0 TERICu305 10.0 20.0 50.0 Water 10.0 10.0 10.0 10.0 SOLVESSOTM 150 To lL To lL To lL To lL 15 RESULTS Table 8 5/95 dilution of Composition IV in Flexi-N®tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30s Nil Nil 9 Nil Poor emulsion Emulsification Emulsion Stability 30 min 4.0 1.5 Nil Nil WO 2007/030885 PCT/AU2006/001353 37 Table 9 5/95 dilution of Composition V in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30s Nil Nil 10 Nil Poor emulsion Emulsification Emulsion Stability 30 min 2.0 3.0 Nil Nil Table 10 5/95 dilution of Comp[osition VI in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mlL) (mL) (mL) Initial 30s Nil Nil 10 Nil good emulsion Emulsification Emulsion Stability 30 rmin Nil Nil Nil Nil Emulsion Stability 2hrs Nil Nil Nil Nil 5 Table 11 5/95 dilution of Composition VII in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30s Nil Nil 8 Nil Very poor emulsion Emulsification Emulsion Stability 30 min 5.0 Nil Nil Nil CONCLUSION Composition VI was found to form a stable mixture when diluted (5%v/v dilution) 10 with Flexi-N
    ®
    . Composition Vllwas found to be incompatible when diluted with Flexi-N ® and Compositions IV and V were significantly less compatible than Composition VI. 15 Example 8 WO 2007/030885 PCT/AU2006/001353 38 This example demonstrates the preparation of an emulsifiable concentrate of an insecticide (alpha-cypermethrin 100g/L) which is compatible when mixed/diluted with Flexi-N ® 5 PROCEDURE Various formulations were prepared (refer to Table 12) and then the formulations were evaluated by diluting/mixing them with Flexi-N ® to evaluate which 10 formulation is compatible with Flexi-N . Table 12: Formulation details Material Composition Composition Composition Composition VIII IX X XI (g) (g) (g) (g) Alpha-cypermethrin 105.3 105.3 105.3 105.3 technical (95%) KEMMAT HF60 40.0 40.0 40.0 40.0 TERIC" N13 20.0 20.0 20.0 20.0 (Nonyl phenol ethoxylate) TERICu 16M15 10.0 10.0 10.0 10.0 (Oleylamine, ethoxylated) TERIC@ 305 10.0 20.0 50.0 (Phosphorylated alcohol ethoxylate) Acetic acid (Glacial) 1.0 1.0 1.0 1.0 SOLVESSOTM 150 TolL TolL TolL TolL 15 RESULTS Table 13 5:95 dilution of Composition VIII in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30 s Nil Nil 7 Nil Poor emulsion Emulsification WO 2007/030885 PCT/AU2006/001353 39 Emulsion Stability 30 min 2.5 3.0 Nil Nil Table 14 5/95 dilution of Composition IX in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30 s Nil Nil 8 Nil Poor emulsion Emulsification Emulsion Stability 30 min 2.2 3.4 Nil Nil Table 15 5:95 dilution of Composition X in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30 s Nil Nil 9 Nil good emulsion Emulsification Emulsion Stability 30 min Nil Nil Nil Nil Emulsion Stability 2 hrs Nil Nil Nil Nil 5 Table 16 5:95 dilution of Composition Xi in Flexi-N® tested at room temperature. Test performed Time Oil Cream Froth Solid Comments (mL) (mL) (mL) (mL) Initial 30 s Nil Nil 5 Nil Very poor emulsion Emulsification Emulsion Stability 30 min 3.0 3.0 Nil Nil 10 CONCLUSION Composition X was found to form a stable mixture when diluted (5%v/v dilution) with Flexi-N ® Composition XI was found to be incompatible when diluted with 15 Flexi-N ® and Compositions VIII and IX were found to be significantly less compatible than Composition X.
    权利要求:
    Claims (23)
    [1] 1. An agrochemical emulsifiable concentrate composition comprising: v). at least one agrochemical active agent; 5 vi). a phosphate ester surfactant; vii). a water immiscible solvent component; and viii). an emulsifier composition comprising (a) an alkylarylsulfonate and (b) a non-ionic emulsifier component. 10
    [2] 2. An agrochemical emulsifiable concentrate composition according to claim 1 comprising: i). at least 10% by weight of the at least one agrochemical active agent; ii). at least 1% by weight of the phosphate ester surfactant; 15 iii). at least 10% by weight water immiscible solvent component; and iv). the emulsifier composition comprises (a) at least 1% by weight of the concentrate of alkylarylsulfonate and (b) at least 1% by weight of the concentrate of the non-ionic emulsifier. 20
    [3] 3. An agrochemical emulsifiable concentrate composition according to any one of the previous claims comprising: i). from10 to 80% by weight of the concentrate of the at least one agrochemical active agent; ii). from 2 to 10% by weight of the concentrate composition of the 25 phosphate ester surfactant; iii). from 10 to 80% by weight of the concentrate of the water immiscible solvent component; and iv). the emulsifier composition comprising (a) from 2 to 10% by weight of the concentrate of the alkylarylsulfonate (b) 1 to 10% by weight 30 of the concentrate of the non-ionic emulsifier. WO 2007/030885 PCT/AU2006/001353 41
    [4] 4. An agrochemical emulsifiable concentrate composition according to any one of the previous claims comprising 10 to 80%, and preferably from 20 to 80% of the one or more actives, from 2 to 10% of the phosphate ester surfactant; from 5 15 to 85% e.g. 30 to 60% of the water immiscible solvent; from 1 to 10% of the alkylarylsulfonate and from 1 to 10% of the non-ionic emulsifier.
    [5] 5. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the phosphate ester surfactant comprises one or 10 more selected from the group consisting of: (vi) alcohol phosphates such as alkyl mono and di-phosphates (eg. N-butyl mono/di-phosphate) and C6 to 0Co10 alkyl phosphate esters; (vii) alcohol ethoxylate phosphates such as C8 to Clo alcohol ethoxylate phosphate esters, tridecyl alcohol ethoxylate phosphate esters, C10o to 15 C15 alcohol ethoxylate phosphate esters, butyl cellosolve phosphate esters, oleyl alcohol ethoxylate phosphate esters; (viii) alkyl phenol ethoxylate phosphates such as nonylphenol ethoxylate phosphate ester and salts thereof and dinonylphenol ethoxylate phosphate ester; 20 (ix) aryl phosphate ethoxylate esters such as phenol ethoxylate phosphate esters; and (x) alkyl amine phosphates such as triethylammonium phosphate.
    [6] 6. An agrochemical emulsifiable concentrate composition according to any 25 one of the previous claims wherein the phosphate ester is selected from the group consisting of Clo to C15 alcohol ethoxylate phosphates
    [7] 7. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the phosphate ester surfactant comprises the 30 phosphonic acid ester formed with lauryl polyglycol ether. WO 2007/030885 PCT/AU2006/001353 42
    [8] 8. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the composition does not give rise to crystalline precipitates upon storage for at least 48 hours at 0°C. 5
    [9] 9. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the non-ionic emulsifier component comprises one or more surfactants selected from the group consisting of the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol; the condensation products of ethylene oxide with phenols and 10 alkylphenols such as isooctylphenol, octylphenol and nonylphenol; the condensation products of ethylene oxide with castor oil; the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate, and their condensation products with ethylene oxide; ethylene oxide/propylene oxide block copolymers; lauryl alcohol polyglycol ether acetal. 15
    [10] 10. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the alkylarylsulfonate component comprises one or more selected from the group consisting of butylnaphthalenesulfonic acid, the di- and tri-isopropylnaphthalenesulfonic acids, the salts of the condensation 20 products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives with phenol and formaldehyde, and the salts of alkylarylbenzenesulfonic acids such as dodecylbenzenesulfonic acid. 25
    [11] 11. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the alkylarylsulfonate is selected from the group consisting of dodecylbenzenesulfonic acid and oil-soluble salts thereof, such as, for example, the calcium salt or the isopropylammonium salt of dodecylbenzenesulfonic acid. 30 WO 2007/030885 PCT/AU2006/001353 43
    [12] 12. An agrochemical emulsifiable concentrate composition wherein the water immiscible solvent component comprises one or more selected from the group consisting of mineral oil fractions such as, for example, kerosene, solvent naphtha, petroleum, coal tar oils and aromatic petroleum fractions; aliphatic, 5 cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin, cyclohexane, tetrahydronaphthalene and alkylated aromatics such as alkylated benzenes and naphthalenes; higher alcohols such as cyclohexanol and octanol; ketones such as, for example, cyclohexanone and isophorone. 10
    [13] 13. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein alkylated aromatics comprise at least 50% by weight of the water immiscible solvent, preferably at least 70% and most preferably at least 80 of the water immiscible solvent component. 15
    [14] 14. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the water immiscible solvent component comprises long chain alkylbenzenes.
    [15] 15. An agrochemical emulsifiable concentrate composition according to any 20 one of the previous claims wherein the water immiscible solvent component comprises acetophenone as a cosolvent.
    [16] 16. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the water immiscible solvent comprises at 25 least 5% by weight acetophenone, preferably from about 5 to about 20% by weight of the emulsifiable concentrate composition of acetophenone.
    [17] 17. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the active agent component comprises at 30 least one selected from the group consisting of dinitroaniline herbicides and phenoxyalkanoate herbicides. WO 2007/030885 PCT/AU2006/001353 44
    [18] 18. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the composition comprises: i). at least one dinitroaniline herbicide selected from trifluralin, pendimethalin and ethalfluralin providing a total dinitroaniline 5 content of from 30% to 70% by weight of the concentrate; ii). from 2 to 10% by weight of the concentrate composition of the phosphate ester surfactant selected from Co10 to C15 alcohol ethoxylate phosphate esters; iii). from 10 to 80% by weight of the concentrate of the water 10 immiscible solvent component comprising alkyl benzenes; iv). the emulsifier composition comprising (a) from 2 to 10% by weight of the concentrate of dodecylbenzene sulfonate surfactant and (b) 1 to 10% by weight of the concentrate of the non-ionic emulsifier comprising condensation products 15 of alkylene oxide.
    [19] 19. An agrochemical emulsifiable concentrate composition according to any one of the previous claims wherein the composition is mixed with a liquid nitrogenous fertilizer selected from urea-ammonium nitrate (UAN) and urea 20 ammonium sulfate (UAS) prior to use.
    [20] 20. A method of applying a agrochemical comprising: providing an emulsifiable concentrate comprising the agrochemical as 25 herein disclosed; combining the emulsifiable concentrate with a liquid nitrogenous fertilizer to form an oil-in-water emulsion having a discontinuous oil phase comprising the water immiscible solvent; and applying the oil in water emulsion to the site of use preferably by spray 30 application. WO 2007/030885 PCT/AU2006/001353 45
    [21] 21. A method according to claim 20 wherein the liquid nitrogenous fertilizer is mixed with the concentrate of the invention in an amount of from about 5% to 500% and preferably 20% to 100% by weight of the active agrochemical component of the concentrate composition. 5
    [22] 22. An agrochemical emulsifiable concentrate according to any one of claims 1 to 19 wherein the active agent comprises at least one herbicides selected from the group consisting of esters of 2,4-D, esters of MCPA, esters of dichlorprop, 10 esters of dichlorprop-P, esters of mecoprop, esters of mecoprop-P, esters of 2,4 DB and esters of MCPB.
    [23] 23. A method according to claim 20 wherein the rate of application of the compositions is from 0.01 to 20 kilograms of active compound component per 15 hectare.
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    同族专利:
    公开号 | 公开日
    AU2006292036B2|2010-12-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4313847A|1978-06-15|1982-02-02|Ici Americas Inc.|Surfactant compositions|
    IT1131750B|1980-06-06|1986-06-25|Montedison Spa|STABLE FORMULATIONS OF N- -N'METOXY-N'-METHYLENE AND 2,6-DINITOR-N, N-DIPROPYL-4-TRIFLUOR METHYLANILINE IN EMULSION|
    法律状态:
    2011-04-14| FGA| Letters patent sealed or granted (standard patent)|
    优先权:
    申请号 | 申请日 | 专利标题
    AU2005905130A|AU2005905130A0||2005-09-16|Herbicide composition|
    AU2005905130||2005-09-16||
    AU2005905131A|AU2005905131A0||2005-09-16|Herbicide composition containing surfactant|
    AU2005905131||2005-09-16||
    US78636506P| true| 2006-03-28|2006-03-28||
    US60/786,365||2006-03-28||
    PCT/AU2006/001353|WO2007030885A1|2005-09-16|2006-09-15|Agrochemical emulsifiable concentrate|
    AU2006292036A|AU2006292036B2|2005-09-16|2006-09-15|Agrochemical emulsifiable concentrate|AU2006292036A| AU2006292036B2|2005-09-16|2006-09-15|Agrochemical emulsifiable concentrate|
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