AGROCHEMICAL SPRAY TREATMENT AND SPRAY FORMULATIONS

Abstract: Plants can be treated by spraying with a formulation including at least one compound of the formula (I): (R<2>)p-Ph-(CH2)m-COO-(AO)n-R<1> (I) where R1, AO, n, m, Ph, R<2> and p have defined meanings, particularly alkyl benzoates, together with at least one surfactant and/or an agrochemical, is sprayed onto the plant or onto the immediate environment of the plant. The compouds of the formula (I) are effective solvents which have low environmental impact. The invention includes spray treating plants with a crop oil formulation based on compounds of the formula (I); and/or herbicides and/or pesticide formulations including compounds of the formula (I).

Description: Agrochemicai Spray Treatment and Spray Formulations This invention relates to the treatment of plants, in particular to the treatment of plants with formulations including certain esters in combination with surfactants and especially to such treatment where the formulations also contain agrochemicals; to agrochemicai formulations in particularly to formulations in which an agrochemicai is dissolved in an ester as solvent or carrier fluid. Carrier fluids or solvents are used in crop protection applications as solvents for formulation components, particularly agrochemicals, particularly in concentrate formulations (for dilution usually in water prior to use) and as adjuvants i.e. materials that are not themselves agrochemicaliy active, but enhance the activity of an agrochemicai, in particular as crop oils, tank mix additives or built into concentrate agrochemicai formulations. Currently carrier fluids or solvents include aromatic hydrocarbons such as xylene and mineral oils, particularly those containing aromatic hydrocarbons such as the "Solvesso" (Exxon Chemicals) and "Shellsol" (Shell Chemicals) ranges and aliphatic and paraffinic solvents such as the "Exxsol" and "Isopar" (Exxon Chemicals) ranges. The present invention is based on the discovery that certain esters of aromatic carboxylic acids, particularly benzoic acid, can be used very effectively in the treatment of plants and in particular as carrier fluids and/or solvents for agrochemicals. the term "agrochemicai" is used to refer to agrochemicaliy active compounds and materials. Such carrier fluids and/or solvents are environmentally much less objectionable than the largely aromatic hydrocarbon materials used currently. The present invention accordingly provides a method of treating plants, in which a composition including at least one compound of the formula (I): (R2)p - Ph - (CH 2 ) m - COO - (AO) n - R 1 (I) where R 1 is a Cι to C20 alkyl or alkenyl group, particularly a C-j to C-^g, more particularly a C-] to Cg alkyl group, especially a C3 to C5 branched alkyl group; AO is an alkyleneoxy group, particularly an ethyleneoxy or a propyleneoxy group, and may vary along the (poly)alkyleneoxy chain; n 0 or from 1 to 100, desirably 0; m is 0, 1 or 2, desirably 0; and Ph is a phenyl group, which may be substituted with groups (R 2 ) p ; where each R 2 is independently a C-( to C4 alkyl or alkoxy group; and p is 0, 1 or 2, desirably 0; together with at least one surfactant and/or an agrochemicai, is sprayed onto the plant or onto the immediate environment of the plant. The method of the invention includes a method of treating plants, particularly fruit trees r .by spraying onto the plants a formulation of a carrier fluid including at least one compound of the formula (I) as defined above; at least one surfactant; and optionally also including at least one agrochemicai, particularly a pesticide, especially an insecticide, desirably dissolved in the carrier. The method of the invention further includes a method of treating plants by spraying onto the plants a formulation which is an aqueous emulsion of a carrier fluid which includes at least one compound of the formula (I) as defined above; at least one agrochemicai; and at least one surfactant. Desirably one or more agrochemical(s) is(are) dissolved in the carrier fluid. The invention includes an agrochemicai formulation which includes a carrier fluid including at least one compound of the formula (I); at least one agrochemicai; and at least one surfactant. In the agrochemicai formulation of the invention desirably at least one of the agrochemical(s) and/or surfactant(s) is dissolved in the carrier fluid, although some materials, agrochemical(s) and/or surfactant(s) and/or other components, may be dispersed in the formulation (in the carrier fluid or other liquid phase components). The carrier fluid may be the major liquid phase of the formulation or it may be emulsified in water. The formulation may thus take the form of solutions, particularly solution concentrates, emulsions, including emulsion concentrates, emulsifiable concentrates, suspensions, oil based suspension concentrates, suspoemulsion concentrates, microemulsions, multiple emulsions, and spray formulations obtained by diluting concentrated formulations, particularly to give solutions, emulsions, suspensions (dispersions) , suspoemulsions, microemulsions or multiple emulsions. The invention specifically includes agrochemicai formulations in the form of one of: a an oil in water emulsion of a solution of at least one agrochemicai in a water immiscible liquid which is or includes at least one compound of the formula (I); and b a water in oil emulsion in which the continuous phase is a solution of at least one agrochemicai in a water immiscible liquid which is or includes at least one compound of the formula (I). The invention also includes: c an emulsifiable concentrate, which is typically diluted with water to form an oil in water emulsion before use, in which at least one agrochemicai is dissolved in a carrier fluid which is or includes at least one compound of the formula (I) and which further includes in solution or dispersion at least one emulsifier surfactant and desirably includes at least one adjuvant surfactant; d an oil based suspension concentrate, which is typically diluted with water to form a suspension (dispersion) of an agrochemicai when diluted in water before use, in which at least one agrochemicai is dispersed in a carrier fluid which is or includes at least one compound of the formula (I) and which further includes in solution or dispersion at least one dispersant surfactant and desirably includes at least one adjuvant surfactant; e a suspoemulsion concentrate (commonly in the art simply referred to as a "suspoemulsion"), which is typically diluted with water to form a suspoemulsion (combined suspension and emulsion) including an agrochemicai in water before use, in which at least one agrochemicai is dissolved in a carrier fluid which is or includes at least one compound of the formula (I), the formulation further including at least one dispersed solid, which may be at least one agrochemicai (generally other than that dissolved in the carrier fluid) and which further includes in solution or dispersion at least one emulsifier and at least one dispersant surfactant and desirably includes at least one adjuvant surfactant; f a microemulsion, which is typically diluted with water to form a diluted microemulsion of an agrochemicai in water before use, in which at least one agrochemicai is dissolved in a carrier fluid which is or includes at least one compound of the formula (I) which is dispersed in an aqueous continuous phase in the form of a microemulsion, and which further includes in solution or dispersion at least one, and usually at least two, emulsifier surfactant(s) and desirably includes at least one adjuvant surfactant; g a multiple emulsion, which is typically diluted with water to form a multiple emulsion formulation containing an agrochemicai in water before use, in which a carrier fluid which is or includes at least one compound of the formula (I) is emulsified in an aqueous phase, the droplets of carrier fluid including emulsified droplets of an inner aqueous phase, the carrier fluid or the inner aqueous phase including at least one dissolved agrochemicai, the multiple emulsion further including at least one, and usually at least two, emulsifier surfactant(s) and desirably includes at least one adjuvant surfactant. The invention further includes diluted versions of the above formulations, usually diluted with water. The invention also includes a method of treating vegetation in which the vegetation is sprayed by a formulation of the invention, particularly a diluted formulation, particularly in the form of an oil in water emulsion or a water in oil emulsion, and/or particularly a diluted emulsifiable concentrate, a diluted suspension concentrate, a diluted suspoemulsion, a diluted microemulsion and/or a diluted multiple emulsion. A further possible way of incorporating agrochemicai active materials in formulations of and used in this invention is as liquids or solutions of the active in a suitable, usually water immiscible, solvent in which are microencapsulated. The water immiscible liquid which is or includes at least one compound of the formula (I) can be or be part of the fluid within which the microcapsules are dispersed and/or it may act as the solvent (when used) for the active within the microcapsules. The microcapsules can be made by conventional methods from an emulsion of the liquid or dissolved active in a, normally aqueous, liquid for example by coacervation, particularly using proteinaceous polymers such as gelatin, in situ polymerisation of e.g. urea and/or melamine formaldehyde polymers, to form the capsule walls, or by interfacial polymerisation. Once microencapsulated, the active is within the bulk of the formulation in substance present as a dispersion and can be formulated as described below. Accordingly, the invention includes: h an agrochemicai formulation including an agrochemicai in microencapsulated form suspended in a liquid formulation including at least one compound of the formula (I); and i a microencapsulated agrochemicai which is a microencapsulated solution of an agrochemicai in a solvent including at least one compound of the formula (I), usually for spray application dispersed in water. The invention further includes the use of compounds of the formula (I), as defined above, as carrier fluids or solvents for agrochemicals. As is discussed below, desirably the carrier fluid is or includes iso-propyl benzoate. In compounds of the formula (I) the group R^ is a is a C-\ to C20 alkyl or alkenyl group, C-\ to C-J Q alkyl group. Desirably R 1 is a C^ to CQ alkyl group, and is desirably branched e.g. it is an iso- propyl (prop-2-yl), sec-butyl (but-2-yl), /so-butyl (2-methyl-prop-1-yl) and/or terf-butyl group, to reduce the ease with which the ester can be hydrolysed. Esters with secondary alcohols are particularly useful in this regard and R 1 is thus especially a C3 to C5 secondary alkyl group and very desirably an /so-propyl group. Although generally desirably, the alkyl group R 1 is a relatively short chain, particularly a C-j to Cg alkyl, group, it may be a longer chain group as in a C5 to C20 alkyl or alkenyl group, particularly a Cβ to C-J S alkyl or alkenyl group which may be straight chain e.g. as in mixed esters such as (mixed C-12/C13 alkyl) benzoate, or branched e.g. as in 2- ethylhexyl or /so-nonyl or branched chain C-|8 alkyl as in so-called /so-stearyl (actually a mixture of mainly branched C-J4 to C22 alkyl with an average chain length close to C-is)- Unsaturated longer chain groups include oleyl. Where longer chain length groups are used, particularly longer than C-j 2. i is desirable that are or include branching and/or unsaturation and/or that mixtures of such esters are used, as these tend to be more liquid than straight chain saturated esters. Although the carboxylic acid used in the ester can be a dihydrocinnamic acid or a phenyiacetic acid, it is very desirably a benzoic acid i.e. desirably m is 0. Similarly, although the phenyl ring of the acid may be substituted, it is desirable that it is unsubstituted i.e. desirably p is 0. The esters used in the invention may include a (poly)alkyleneoxy chain, (AO) n in formula (I), between the carboxyl group and the group R 1 . When present the (poly)alkyleneoxy chain is desirably a (poly)ethyleneoxy, a (poly)propyleneoxy chain or a chain including both ethyleneoxy and propyleneoxy residues. Generally, it is desirably not to include such a chain in the ester i.e. desirably n is 0. A particularly useful ester is /so-propyl benzoate and the invention specifically includes a method of treating vegetation, particularly by spraying and agrochemicai formulations and methods, in which /so-propyl benzoate is used as a solvent, carrier fluid or crop oil. /so-propyl benzoate has a combination of properties that make it exceptionally useful in these roles. As a pure material, it has a wide liquid range (boiling point ca 219°C and pour point < -60°C), is classified as non-flammable (flash point ca 99°C), with a low vapour pressure under normal use conditions; a similar density to water (1.008 kg.l "1 at 25°C); and a low viscosity (2.32 cSt at 25°C; measured by the U tube method, equivalent to 2.34 mPa.s). Desirably, the carrier fluid used in formulations of the invention is wholly of one or more compounds of the formula (I). However, if desired other solvents or carrier fluids may be used in admixture. Examples of other such fluids include mineral oil, vegetable oil, propylene tetramer and ethyl lactate. Although oils containing aromatic hydrocarbons can be included it is unlikely that they will be used as a major component of any such mixed carrier fluid, because of the likely adverse environmental impact. When mixtures are used, the compound(s) of the formula (I) can be used as co-solvents, or solvency improvers, or as the principal solvent or carrier fluid in the formulation. When used as co-solvents, the proportion of the compound(s) of the formula (I) used in the solvent will usually be from 0.5 to 25%, more usually from 1 to 10%, and particularly from 1 to 5%, by weight of the solvent, with the remaining carrier fluid or solvent materials being from 99.5 to 75, more usually from 99 to 90% of the carrier fluid or solvent. When used as a or the principal solvent the proportion of the compound(s) of the formula (I) used in the solvent will typically be present as at least 25%, usually at least 40%, more usually at least 50%, desirably at least 60%, and particularly at least 75%, by weight of the total carrier fluid used with the other carrier fluid components or solvents (when present) typically from 1 to 75%, usually from 1 to 60%, more usually from 2 to 40%, desirably 3 to 25%, and particularly 5 to 15% by weight of the total carrier fluid used. The compounds of the formula (I) can be used as or in crop oils either for crop oils in agrochemicai formulations where they can provide beneficial effects on the performance of the agrochemicals (somewhat similar overall effects to adjuvants) or for crop oil sprays where the oil itself functions to provide beneficial effects on crops, particularly fruit trees as in winter oil spraying, so treated. When used for crop oil sprays the spray formulation will generally include at least one surfactant material, particularly to improve wetting and/or spreading of the crop oil on the crop plants sprayed. The crop oil can be sprayed as a neat oil formulation or as an emulsion of the crop oil in water. The compounds of the formula (I) can also be used as solvents for other components of agrochemicai formulations, particularly for water insoluble active agrochemicals. When used as solvents for agrochemicals, the active agrochemicai can be of a wide range of materials. In particular, the agrochemicaliy active component of the formulation may be one or more plant growth regulators, herbicides, and/or pesticides, for example insecticides, fungicides, acaricides, nematocides, miticides, rodenticides, bactericides, molluscicides and bird repellants. Generally, when water soluble actives are used the esters of the formula (I) will be included primarily as crop oils or adjuvants, and where water insoluble actives are used the esters of the formula (I) will b© included primarily as solvents or carrier fluids for the active. When the agrochemicaliy active component is water soluble, the compound(s) of the formula (I) will usually be used as a crop oil or oil adjuvant in the formulation. Typical water soluble actives are water soluble herbicides, particularly non-selective, herbicides including phosphonomethyl glycines such as Glyphosate and Sulfosate {respectively the /so-propylamino and trimethylsulphonium salts of Λ/-phos- phonomethyl glycine}; phosphinyl amino acids such as Glufosinate {2-amino-4- (hydroxymethyl-phosphinyl) butanoic acid} particularly as the ammonium salt and bipyridinium compounds such as Paraquat {1 ,1 '-dimethyl-4,4'-bipyridinium}. Among water soluble active materials particularly suitable actives include, non-selective herbicides, particularly Λ/-(phosphono- methyl) glycine type herbicides, such as Glyphosate and Sulfosate and phosphinyl amino acids, such as Glufosinate, particularly as the ammonium salt. When actives which are not water soluble are included in the formulation, the compound(s) of the formula (I) will usually be used as solvents for the actives. Actives which can be used in this type of formulation include: ' Herbicides including: triazines such as atrazine {6-chloro-A/-ethyl-N'-(1-methylethyl)-1 ,3,5-triazine-2,4-diamine, and prometryn {Λ/,Λ -bis(1 -methylethyl)-6-(methylthio)-1 ,3,5-triazine)-2,4-diamine}; substituted ureas such as diuron {W-(3,4-dichlorophenyl)-W,Λ/-dimethylurea}; sulphonyl ureas such as metsulfuron-methyl {2-[[[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl) amino]carbonyl]amino]sulfonyi]benzoate}, triasulfuron {2-(2-chloroethoxy)-Λ/-[[(4-methoxy- 6-methyl-1 ,3,5-triazin-2-yl)amino]carbonyljbenzenesulfonamide}, tribenuron-methyl {methyl 2-[[[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)-methylamino]carbonyl]amino]sulfonyl] benzoate} and chlorsulfuron {2-chloro-Λ/-[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)amino] carbonyljbenzenesulfonamide}, bis-carbamates such as phenmedipham {3-[(methoxy-carbonyl)amino] phenyl (3- methylphenyl)carbamate}; pyridine carboxylic acids such as clopyralid {3,6-dichloropyridine-2-carboxylic acid}; aryloxy alkanoic acids such as 2,4-D {2,4-dichlorophenoxyacetic acid}; and 2-(4-aryloxyphenoxy)propionic acids such as clodinafoppropargyl {prop-2-ynii (R)-2-[4-(5-chloro-3-fluoropyridinr-2-yloxy) phenoxy]-propionate}. Fungicides: including thiocarbamates, particularly alkylenebis(dithiocarbamate)s, such as maneb {[1 ,2-ethanediylbis- [carbamodithiato] (2-)] manganese} and mancozeb {[[1 ,2-ethanediyl- bis[carbamodithiato]j (2-)]manganese mixture with [[1 ,2-ethanediylbis[carbamodithiatoj] (2-)jzinc}; strobilurins such as azoxystrobin {methyl (E)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxyj- a-(methoxymethylene)benzeneacetate} and kresoxim-methyl {(E)-a-(methoxyimino)- 2-[(2-methylphenoxy)methyl]benzeneacetic acid methyl ester}; dicarboximides such as iprodione {3-(3,5-dichlorophenyl)-Λ/-isopropyl-2,4-dioxo imidazolidine-1- carboxamide}; benzimidazoles such as carbendazym {methyl benzimidazol-2-yl carbamate}; azoles such as propiconazole {1 -[2-(2,4-dichlorophenyl)-4-propyl-1 ,3-dioxolan-2-yl-methyl-1 H- 1 ,2,4-triazole}, and tebuconazole {(RS)-1-p-chlorophenyl-4,4-dimethyl- 3-(1 H-1 ,2,4-triazole-1-ylmethyl)-pentan-3-ol}; halophthalonitriles such as chlorothalonii {2,4,5,6-tetrachloro-1 ,3-dicyanobenzene}; and inorganic fungicides such as Copper hydroxide {Cu(OH)2}; Insecticides: including benzoyl ureas such as diflubenzuron {N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluoro- benzamide)}; pyrethroids such as cypermethrin {cyano(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2- dimethylcyclopropanecarboxylate}; and organophosphates such as chlorpyrifos {0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl) phosphorothioate}; Acaricides including: tetrazines such as clofentezine {3,6-bis(2-chlorophenyl)-1 ,2,4,5-tetrazine}. Combinations of more than one active including more than one type of active may be used if desired. Thus where water soluble actives are used, they may be dissolved in an aqueous phase in the formulation and a further active can be included in dispersed form or in solution in the carrier fluid. In particular, formulations can be made up using a water soluble (non-specific) herbicide such as Glyphosate, Sulfosate and/or Glufosinate, with a selective herbicide, such as a sulphonyl urea e.g. metsulfuron-methyl, pyridine carboxylic acid e.g. clopyralid, aryloxy alkanoic acids e.g. 2,4-D, substituted ureas e.g. diuron, or 2-(4-aryloxyphenoxy)propionic acids e.g. clodinafoppropargyl, and/or with an insecticide and/or fungicide, in particular where the other active is dissolved in the carrier fluid. The surfactant(s) included in the composition of and used in the invention can serve a variety of purposes including as wetting agents, emulsifiers, dispersants and adjuvants. Wetting agents ("wetters") can be nonionic surfactants such as alcohol ethoxylates e.g. of Cg to Ci 5, particularly primary, alcohols, which may be linear, branched or mixtures of linear and branched, particularly mono-branched, with from 5 to 30 moles of ethylene oxide; and alkoxylates of such alcohols particularly mixed ethoxylate/ propoxylates which may be block or random mixed alkoxylates, typically containing from 3 to 10 ethylene oxide residues and from 1 to 5 propylene oxide residues, particularly where the polyalkoxylate chain is terminated with propylene oxide unit(s); polyoxyethylene/polyoxypropylene copolymers, particularly block copolymers, such as the Synperonic PE series of copolymers available from Uniqema, and alkyl polysaccharides; silicone based surfactants; anionic surfactants e.g. isethionates, such as sodium cocoyl isethionate, naphthalene sulphonic acids or sulphosuccinates. Emulsifiers can be anionic surfactants e.g. alkali metal or alkali earth metal salts of sulphonated hydrocarbons such as alkyl benzene sulphonates particularly Ca dodecylbenzene sulphonate; and/or non-ionic surfactants including alcohol alkoxylates such as those based on C3 to C22 > particularly C-12 to C-|8 > alcohols, which may have straight or branched, usually alkyl, chains, and which are alkoxylated with ethylene oxide, propylene oxide or copolymeric chains including residues of both ethylene oxide and propylene oxide, which may be block or random (statistical) copolymeric chains, commercially available examples include: Atlas G-5000, Atlox MBA 1306 and Synperonic A11 to A20 available from Uniqema; polyalkoxylated fatty acids based on Cs to C22. particularly C-)2 to C^ Q, fatty acids; sorbitan and sorbitol esters, e.g. sorbitan monolaurate and monooleate; poly(alkoxylated) derivatives of sorbitan and sorbitol esters; and poly(alkoxylated) fatty amines such as tallow amine ethoxylates. The ranges of non-ionic surfactants can encompass both water in oil and oil in water emulsifiers; generally the former have relatively long hydrophobes and/or small hydrophiles, particularly polyethylenoxy, chains and the latter have relatively shorter hydrophobes and/or larger hydrophiles. Dispersants (dispersing agents) for dispersing solids in water include naphthalene sulphonate formaldehyde condenses e.g. as sodium and ammonium salts; sodium, lignosulphonates e.g. as calcium and ammonium salts; maleic anhydride copolymers e.g. as sodium and ammonium salts; condensed phenolsulphonic acid e.g. as sodium salts; sulphonated polystyrenes; acrylic acid styrene copolymers; and acrylic graft copolymers, particularly with polyethylene glycols; and for dispersing solids in oil phases or solvents condensed fatty acid surfactants such as polycondensed fatty acids and/or their quaternary ammonium and/or alkaline earth metal and/or amine derivatives and polyamine / fatty acid condensate solutions; polyoxyalkylene amine derivatives; polyester polyether block copolymers; and polyaikylene glycol ethers. Adjuvants can be non-ionic surfactant adjuvants such as the so-called hydrocarbyl, particularly alkyl e.g. C5 to C-14, especially from 03 to C-12 alkyl, polysaccharides (generally more correctly described as oligosaccharides), typically having an average of from 1 to 3, more usually from 1.3 to 2 saccharide units in the oligosaccharide chain; hydrocarbyl, particularly alkyl, amine alkoxylates, particularly ethoxylates; linear or mono-branched (or mixed) alcohol alkoxylates, particularly ethoxylates; sorbitol and sorbitan fatty acid esters and their alkoxylated, particularly ethoxylated derivatives. Further adjuvants include amphoteric surfactants such as betaines and cationic surfactants such as long chain alkyl e.g. C-|2 to C22. particularly C14 to C<|8 alkyl, quaternary ammonium compounds. Coadjuvants, such as ionic and/or inorganic materials, for example ammonium sulphate, may be included in adjuvant containing agrochemicai formulations of the invention, particularly with non-ionic surfactant adjuvants. The proportions of materials used in formulations of and used in this invention depend on the intended end use and a range of these are described below. In these the terms "solvent" and "carrier fluid" refer to an organic solvent or carrier fluid which includes at least one compound of formula (I), particularly /sopropyl benzoate and "emulsifiers", "dispersants", "wetters" and "adjuvants are particularly materials as described above. For formulations not themselves including active agrochemicals, particularly crop oils, typical compositions include: For crop oil use such compositions can be applied neat or diluted (emulsified) in water. When used neat, typically they will be applied as so called "winter oil" sprays on e.g. fruit trees, typically at from 0.1 to 10 l-ha "1 , more usually from 1 to 3 I. ha "' ' . In such neat formulations the surfactant(s) will usually function as a wetters including to aid spreading and penetration of the oil over or into the bark of treated plants particularly trees. When used after dilution in water the rate of dilution is typically from 1 to 10000 times, more usually from 10 to 1000 times, by volume. Such diluted formulations will typically be sprayed at from 10 to 500 l.ha "' ' , more usually from 50 to 300 l.ha" 1 . In formulations for dilution to form emulsions, the surfactant(s) will usually include emulsifier(s) and may also include wetter(s). For formulations including active agrochemicals, the compositions will depend on the form of the formulation, particularly for concentrate formulations. In principle, spray formulations including compounds of the formula (I) can be made up in situ in the spray tank from the individual components. However, this is generally not convenient as it requires the end user to have suitable (relatively high intensity) mixing equipment. More usually the agrochemicai and surfactant components will be incorporated in preformulated compositions which can be diluted with water at the point of use to form sprayable formulations requiring no or only moderate mixing. Emulsifiable concentrates are oil based concentrates which on dilution with water spontaneously or very readily form oil in water emulsions, typically of an agrochemicai dissolved in an oil, in the water phase. They are also sometimes described as "built-in concentrates". The surfactant(s) in emulsion concentrates act(s) to form a homogeneous concentrate that readily or spontaneously emulsifies on dilution into water. The surfactant is often a combination of two or more surfactant compounds including emulsifiers to stabilise the emulsion formed on dilution and may also include adjuvant surfactants. Typical ranges for the main components of emulsifiable concentrates are: Oil based suspension concentrates are used to disperse oil insoluble active ingredients which are also water insoluble or are too water soluble to include in a water based flowable or are not chemically stable in water. Such formulations will also usually include dispersant surfactant(s), particularly condensed fatty acid surfactants, and they also usually include emulsifier(s) to emulsify the carrier fluid phase on dilution into water. Such formulations may also include adjuvants. On dilution into water a water insoluble solid active may become dispersed directly in water or may be a solid dispersed phase in the emulsified oil phase (this is very similar to suspoemulsions on dilution see also below). Overall the composition of oil based concentrates is typically as set out below: Agrochemicai suspoemulsion concentrates are formulations which on dilution (in water) give suspoemulsions i.e. which include at least one liquid (emulsion) disperse phase and at least one solid disperse phase, in a continuous aqueous phase. The concentrate formulation can itself be a suspoemulsion, in effect just more concentrated (having less water) than the diluted (spray) formulation; or it may be a dispersion of a solid disperse phase in an emulsifyable concentrate, which on dilution forms an emulsion. They are particularly suitable for agrochemicai formulations which include an oil soluble active, present as a solution in the oil emulsion disperse phase, and a solid water insoluble (and usually also oil insoluble) active, i.e. the solid components usually include an agrochemicai active, present as dispersed particles, although other formulation components may also be present as dispersed solid particles. The solid dispersed phase may be dispersed within the oil based emulsion droplets. Suspoemulsions are typically based on an oil solution of one agrochemicai also including a solid water insoluble active or other solid component present as dispersed particles. They usually include surfactant(s) as emulsifiers, particularly oil in water emulsifiers, to stabilise the emulsion formed on dilution in water to normal spray concentration, and as dispersant for the solid particles in the oil phase and/or the aqueous phase. Suspoemulsion concentrates are typically diluted in water for spray application to form suspoemulsions. Overall the composition of suspoemulsion concentrates are typically as set out below: Microemulsions are thermodynamically stable, transparent concentrate formulations which include a liquid dispersed emulsion phase with a droplet size fine enough not to scatter visible light e.g. less than 0.1 μm. They include surfactants to stabilise the microemulsion particularly emulsifiers and may also include adjuvants. Microemulsions are typically diluted into water usually to form microemulsion spray formulations (formulations that form emulsions are more usually designated as emulsifiable concentrates) before spraying. Overall typical microemulsion compositions are as set out below: Agrochemicai multiple emulsion formulations are concentrate formulations in which a dispersed emulsion phase has within its droplets a dispersion of droplets of another liquid. There are thus two emulsions an outer emulsion and an inner emulsion and the phases can be described as outer and inner external and internal phases. There are two basic types of multiple emulsion: water in oil in water (W/O/W) and oil in water in oil (O/W/O), although W/O/W emulsions are more likely to be used in this invention. A typical W/O/W multiple emulsion will have from 10 to 80%, more usually 20 to 60%, particularly 30 to 50%, by weight internal water in oil (W/O) emulsion and correspondingly 90 to 20%, more usually 80 to 40%, particularly 70 to 50%, by weight external water phase. The internal W/O emulsion will typically include from 1 to 30% by weight water in oil emulsifier and from 20 to 90% by weight of oil phase including a compound of the formula (I) (as defined above). The external water phase will typically include a further 1 to 10% oil in water emulsifier. In using multiple emulsions in this invention, . typically at least on oil soluMe agrochemicai will be dissolved in the oil phase. Other active materials can be water soluble actives dissolved in either the inner water internal phase or in the external water phase, or insoluble actives dispersed in the multiple emulsion. Multiple emulsion formulations are typically diluted into water usually to before spraying. Overall the composition of agrochemicai multiple emulsions are typically as set out below: The compounds of the formula (I) can be included in agrochemicai spray formulations by additions to the aqueous based tank mix, in effect immediately before spraying. In such situations, the addition will usually be as a crop oil that acts to improve the overall effectiveness of the agrochemicai spray. The proportion of the crop oil used in this way is typically from 0.02 to 2 %, more usually from 0.2 to 1%, by weight of the overall spray formulation. The formulation will usually include emulsifier surfactant to aid dispersion of the crop oil as an emulsion in the spray formulation. The compounds of the formula (I) can be used alone or in combination with other crop oils, usually within the composition ranges set out above for oil mixtures. For tank addition in this way, the oil, including the compounds of the formula (I), may also include some or all of the adjuvant surfactant added to the spray formulation and in this approach the oil acts as a carrier fluid (or solvent) for the adjuvant surfactant (as well as potentially as a crop oil). Overall the typical composition of such crop oil / carrier fluid systems are as set out below: Concentrated forms of agrochemicai formulations, including adjuvant concentrates, are usually diluted with water to make sprayable diluted aqueous formulations. Typically the dilution rate is from 10 to 10000, particularly 30 to 1000, times by volume. The dilution rate is chosen to match the required spray volume to the desired application rate of the agrochemicai formulation. The invention includes a method of making a diluted agrochemicai formulation for spraying (spray tank mix) which includes diluting a concentrate containing at least'one active agrochemicai, particularly one or more emulsion concentrate, emulsifiable concentrate, suspension concentrate, suspoemulsion concentrate, microemulsion and/or multiple emulsion, which concentrate also includes at least one compound of the formula (I) with water. The invention also includes a method of making a diluted agrochemicai formulation for spraying (spray tank mix) which includes mixing in any order: a a concentrate containing at least one active agrochemicai, particularly one or more emulsion concentrate, emulsifiable concentrate, suspension concentrate, suspoemulsion concentrate, microemulsion and/or multiple emulsion, which concentrate desirably also includes at least one compound of the formula (I); b a solution of an adjuvant surfactant in a carrier fluid including at least one compound of the formula (I); and c water, particularly in an amount of from 10 to 10000 times by volume of the combined volume of components a and b; to form the diluted agrochemicai formulation. The application rate of diluted formulations, where the bulk of the spray is dilution water, is typically from 50 to 500, more usually from 50 to 400 and commonly about 300, l(spray formulation). ha "1 (crop treated). For more concentrated forms of spray e.g. as in neat winter crop oil spraying or ultra low volume spraying, the application rate may be significantly lower typically 0.5 to 50, more usually 1 to 10, l(spray formulation), ha "1 (crop treated). In agrochemicai sprays, particularly as diluted water based sprays, the concentration of the active agrochemicai is typically from about 0.001 to about 3%, more usually from 0.1 to about 0.5 and particularly about 0.2% by weight of the spray formulation. When used the typical concentration of adjuvant is from 0.02 to about 2%, more usually 0.2 to about 1% and particularly abo it 0.1 %. Typically the weight ratio of active agrochemicai to adjuvant is usually from 1 :100 to 10:1 , more usually from 1 :10 to about 4:1. These figures correspond to crop application rates of the active agrochemicai generally in the range 0.5 to 4000 g.ha "1 , more usually from 3 to about 2000 g.ha" 1 (the actual amount depending on the particular crop, agrochemicai and effect desired). For low volume spraying, generally higher spray concentrations will be used, but the ratio of agrochemicai to adjuvant will be within the ranges given above. Other potential components of agrochemicai formulations of and used in this invention include: thickeners or rheology modifiers are commonly used in liquid concentrate formulations, to stabilise the concentrate against settling, flocculation or phase separation prior to dilution. The amount of thickener used is typically from 0.01 to 5% by weight of the formulation, antifoams, particularly silicon based materials such as organopolysiloxanes, typically used in ' an amount from 0.1 to 10%, preferably 0.2 to 6% by weight of the surfactant; 0.01 to 5%, particularly 0.02 to 2% by weight of agrochemicai concentrate and 0.0001 to 0.1% preferably 0.001 to 0.05% by weight of a spray formulation at end use dilution; viscosity modifiers, particularly gums such as xanthan gums; cellulose derivatives, such as carboxyl-methyl, -ethyl, or -propyl cellulose, typically used at from 0.01 to 5 wt % of a concentrated formulation; and other non surfactant materials such as stabilisers and/or anti-microbials, typically used at from 0.01 to 5 wt % of a concentrated formulation, cold stabilisers, particularly mono propylene glycol, typically used at from 5 to 20 wt % of a concentrated formulation. The following Examples illustrate the invention. All parts and percentages are by weight unless otherwise stated. Materials Actives Act1 malathion ex Cheminova (usually as 66% by wt in CSol2, Xylene or CSol 6) Act2 propargite ex Uniroyal (usually as 36% by wt in Xylene) Act3 trifluralin ex Dow Agrosciences (usually as 55% by wt in Xylene) Act4 acetochlor ex Monsanto (usually as 52% by wt in Xylene) The actives as used were solids (assumed 95+% active). The normal solvent and concentration used for making agrochemicai formulations is indicated above in brackets. Surfactants Surfl Atlox 4838B - Calcium alkyl aryl sulphonate in ethyl hexanol ex Uniqema Surf2 Atlas G1086 - POE sorbitol hexaoleate ex Uniqema Surf3 Atlox 5405B - mixture of anionic and nonionic surfactants ex Uniqema Surf4 Atlox 5406B - mixture of anionic and nonionic surfactants ex Uniqema Surf5 Atlas G5000 - polyalkylene glycol ether non-ionic surfactant ex Uniqema Surf6 Atlox 4912 - polyester polyether block copolymeric non-ionic surfactant ex Uniqema Surf? Atlox 5023 - mixture of anionic and nonionic surfactants ex Uniqema Solvents Soli /so-propyl benzoate 5012 ethyl benzoate 5013 2-ethylhexyl benzoate 5014 nonyl benzoate CSol1 Solvesso 200 - aromatic solvent ex Exxon Chemicals CSol2 Solvesso 150 - aromatic solvent ex Exxon Chemicals CSol3 Solvesso 100 - aromatic solvent ex Exxon Chemicals CSol4 Exxsol D 100 - aliphatic solvent ex Exxon Chemicals CSolδ Isopar L - /soparaffinic solvent ex Exxon Chemicals CSol 6 Shellsol A - aromatic solvent ex Shell Chemicals Other Materials 342 water water with a WHO hardness of 342 ppm Storage (ageing) conditions Some samples were stored (aged) to observe behaviour after storage. In the Examples, the extent of ageing is indicated by a code. The first two characters indicates the length of storage a number followed by a letter: "d" = day; "w" = week; and "m" = month, ("0" = no ageing), and any remaining characters indicate the (non-ambient) storage temperature in °C; so, for example, '1 m/50' indicates 1 month storage at 50°C and '2w-5' indicates 2 months storage at -5°C. Example 1 The effectiveness of /sopropyl benzoate (Soli ) as a solvent for agrochemicai actives was tested. Solid samples (95+% active material) of four actives normally supplied in highly aromatic solvents were dissolved in the Solvent at the usual concentrations (by weight on the solution) of the agrochemicai as supplied for formulation. Soli was used successfully for this without difficulty as shown by the results in Table 1 which show the appearance of the solutions after storage under various conditions. Table 1 These results indicate that sopropyl benzoate can be used to replace a variety of aromatic solvents used conventionally as solvents for agrochemicai actives. For trifluralin, acetochlor and propargite some impurities precipitated from solution at ambient temperature. Samples stored at lower temperatures gave no additional precipitation confirming that the active remained in solution. Similar testing with other solvents gave the results set out in Table 1 ' below. Table l' * Active dissolves giving a slightly hazy solution Example 2 Surf3 was dissolved in Soli to give a solution containing 17% by weight of the surfactant. The appearance of this formulation was assessed fresh and after storage. The fresh and stored solutions were used to make emulsions at 2% by weight in 98% by weight of 342 water at ambient temperature (ca 23°C) by mixing the surfactant solution with water and inverting the mixture 10 times. Emulsion stability was assessed 2 hours ("2h") and 24 hours ("24h") after emulsification and on re-emutsification after 24 hours storage ("re") using surfactant solvent formulation fresh and after storage under various conditions. The results are set out in Table 2 below: Table 2 * NS = no separation, TOC = trace oily cream TC = trace of creaming The emulsions are suitable for spraying as a crop oil and with the inclusion of an oil soluble agrochemicai for agrochemicai spray application. Example 3 Emulsions of Soli were made up for evaluation using the following formulation: Soli 45% wt Surfδ 2.5% wt Surfθ 2.5% wt Water 50% wt (balance) The surfactant was melted and added to the solvent at ca 50°C. The water was heated separately to ca 50°C and the IPB and surfactant added to the water with stirring (250 rpm; ca 4.2Hz). Subsequently, the formulation was homogenised using a high energy stirrer (such as a Silverson or Ultra Turax homogeniser) and then allowed to cool to ambient temperature under stirring. The solvent formulations were used to make emulsions and tested for emulsion stability as described in Example 2 above. The results are set out in Table 3 below: Table 3 NS = no separation TC = trace of creaming These data show that good emulsions can be obtained even with surfactant/solvent formulations that are stored. Example 4 Emulsions of various solvents were evaluated for phytotoxicity at solvent concentrations of 0 (blank), 1 , 10, and 50% solvent in the emulsion. The formulations are set out in Table 4a below and the results of phytotoxicity testing in tomatoes and wheat are summarised in Table 4b below. Table 4a Table 4b coding key: 1 = healthy 2 = slight toxic symptoms 3 = moderate toxicity 4 = severe toxicity 5 = very severe toxicity 6 = dead These data indicate that the phytotoxicity of /sopropyl benzoate is slightly lower than that of aromatic solvents having similar volatility (Solvesso 150 and 200). Example 5 A test emulsifiable concentrate was made up using Soli in the following formulation: Material parts by wt Act3 40 Soli 50 Emulsification and emulsion stability of this concentrate were tested under temperature conditions designed to highlight any crystal growth upon dilution. The concentrate was mixed with 342 water at 0°C or at 30°C to give a 2% dilution - initial emulsification performance was good to excellent - the concentrate gave perfect self emulsification with no signs of separate droplets breaking away. After storage (1m 40°C) the emulsification performance was good - close to perfect self emulsification - only a few droplets tending to break away. Emulsion stability was tested and the results set out in Table 5 below. No crystal growth was noted for any of the dilutions at 0° or at 30°C. Table 5 * temperature of dilution water ** re-emulsification by shaking emulsion 24 hours after initial emulsification Example 6 Concentrated emulsions were made up using the following formulations: 6.1 6.2 Material parts by wt Material parts by wt Soli 45 Soli 45 Surf5 * 2.5 Surfl 2.5 water to 100 water to 100 * these surfactants could be added to the water phase before mixing. The surfactants were melted and added to the solvent at about 50°C. The water was heated to about 50°C and the solvent/surfactant blend added to the water with stirring (250 rpm; ca 4.2 Hz). The emulsion was subsequently homogenised with a high energy stirrer (Silverson or Ultra Turrax) and then allowed to cool to ambient temperature under stirring. The emulsification performance of the formulations - on making a 2% dilution with 342 water at ambient temperature - was assessed after storage and the stability of the emulsions made was assessed was assessed after 2 and 24 hours. All the emulsions had a good white appearance. The results are set out in Table 6 below. Table 6 NS = no separation Note Formulation 1 thickened when stored at -5 °C, but this disappeared on warming to ambient temperature. This is believed to be linked to the surfactant used (probably Surfδ). Example 7 Spray oils were made up using the following formulation: Material parts by wt Soli 83 Surfl 9.35 Surf7 7.65 The physical stability (compatibility) of the formulations was assessed after storage; emulsification was assessed by making a 2% dilution with 342 water at ambient temperature and the stability was assessed after 2 and 24 hours. All the emulsions had a good white appearance. The results are set out in Table 7 below. Table 7

Claims: Claims 1 A method of treating plants, in which a composition including at least one compound of the formula (I): (R 2 )p - Ph - (CH 2 ) m - COO - (AO) n - R 1 (I) where R-j is a C-| to C-|o alkyl group; AO is an alkyleneoxy group and may vary along the (poly)alkyleneoxy chain; n 0 or from 1 to 100; m is O, 1 or 2; and Ph is a phenyl group, which may be substituted with groups (R 2 ) p ; where each R 2 is independently a C-\ to C4 alkyl or alkoxy group; and p is 0, 1 or 2; together with at least one surfactant and/or an agrochemicai, is sprayed onto the plant or onto the immediate environment of the plant. 2 A method as claimed in claim 1 wherein R 1 is a C-j to CQ alkyl group. 3 A method as claimed in claim 2 wherein R 1 is a C3 to C5 branched alkyl group. 4 A method as claimed in any one of claims claim 1 to 3 wherein n is 0, m is 0 and p is 0. 5 A method as claimed in claim 4 wherein the carrier fluid is or includes /so-propyl benzoate. 6 A method as claimed in any one of claims 1 to 5 wherein the at least one agrochemicai includes at least one herbicide, fungicide, insecticide and/or acaricide. 7 A method as claimed in any one of claims 1 to 6 wherein the carrier fluid or solvent includes at least 25% by weight of the total carrier fluid or solvent of a compound of the formula (I). 8 A method as claimed in any one of claims 1 to 7 in which the formulation takes the form of a solution concentrate, an emulsion concentrate, an emulsifiable concentrate, a suspension concentrate, a suspoemulsion concentrate, a microemulsion and/or a multiple emulsion, diluted with from 10 to 10000 time by volume of water. 9 A method as claimed in any one of claims 1 to 5 for treating fruit trees by spraying onto the fruit trees plants a formulation of a carrier fluid including at least one compound of the formula (I) and at least one surfactant. 10 A method as claimed in claim 9 in which the fruit trees are sprayed when they are not carrying leaves. 11 A method as claimed in either claim 9 of claim 10 in which the formulation is a solution of the surfactant in the carrier fluid. 12 A method as claimed in either claim 9 of claim 10 in which the formulation is an emulsion of he carrier fluid in water. A method as claimed in any one of claims 9 to 13 in which the formulation additionally includes an insecticide dissolved in the carrier fluid. An agrochemicai emulsion composition which includes an agrochemicai dissolved in a carrier fluid including at least one compound of the formula (I) emulsified in an aqueous phase and at least one surfactant. An agrochemicai composition as claimed in claim 14 in the form of an emulsion concentrate, an emulsifiable concentrate, an oil based suspension concentrate, a suspoemulsion concentrate, a microemulsion and/or a multiple emulsion. A diluted agrochemicai composition made by diluting an agrochemicai emulsion as claimed in either claim 14 or claim 15 with from 10 to 10000 time by volume of water. A method of making a diluted agrochemicai formulation which includes mixing in any order: a a concentrate containing at least one active agrochemicai, particularly one or more emulsion concentrate, emulsifiable concentrate, suspension concentrate, suspoemulsion concentrate, microemulsion and/or multiple emulsion, which concentrate desirably also includes at least one compound of the formula (I); b a solution of an adjuvant surfactant in a carrier fluid including at least one compound of the formula (I); and c water, particularly in an amount of from 10 to 10000 times by volume of the combined volume of components a and b; to form the diluted agrochemicai formulation. A method of treating plants which comprises spraying the plant or the immediate environment of the plant with a diluted agrochemicai formulation as claimed in claim 16 or made by the method claimed in claim 17.

Inventors: ROMMENS JOHAN CAMIEL GABRIELLE, TANDT YOURY DEN, ROMMENS, JOHAN, CAMIEL, GABRIELLE, TANDT, YOURY, DEN
Applicants: ICI PLC, ROMMENS JOHAN CAMIEL GABRIELLE, TANDT YOURY DEN, IMPERIAL CHEMICAL INDUSTRIES PLC, ROMMENS, JOHAN, CAMIEL, GABRIELLE, TANDT, YOURY, DEN
Application year: 2001
Main classification: A01N25
IPC codes: A01N25