EA041806B1 - PESTICIDE COMPOSITION CONTAINING ALCOHOL ALKOXYLATE CARBONATES, ITS MANUFACTURING METHOD, CONTROL METHOD, SEEDS AND THE APPLICATION OF SPECIFIED ALKOXYLATES TO IMPROVE PESTICIDE EFFICIENCY - Google Patents

Description

The present invention relates to a pesticide composition containing a pesticide selected from a herbicide and an insecticide and an alkoxylate of formula (I),

R^AOVO-CXOl-O-EAO^-R ² (I), where R ¹ and R ² independently represent a C6-C32 hydrocarbon group, AO ¹ and AO ² independently represent a C2-C ₆ alkyleneoxy group, and n and m is independently a value from 2 to 100, provided that the pesticide does not include fungicides. In addition, the invention relates to a process for the manufacture of said composition by bringing into contact an alkoxylate and a pesticide. Ultimately, the invention relates to a method for controlling the growth of unwanted plants and/or unwanted attack by insects, by the action of said pesticidal composition on the respective pests, their habitat or crop plants to be protected from the respective pest, on the soil and/ or undesirable plants and/or their habitat; to seeds containing the specified composition, and the use of an alkoxylate of the specified formula to improve the effectiveness of the pesticide.

Preferred embodiments of the invention, which are mentioned here below, should be understood as being preferred either independently of each other or in combination with each other.

Adjuvants are important agrochemical formulation adjuvants and help improve formulation stability and pesticide efficacy. An ongoing need is to provide new adjuvants with improved properties.

The aim of the present invention was to overcome the problems of the state of the art. The problem was solved using a pesticide composition containing a pesticide selected from a herbicide and an insecticide and an alkoxylate of formula (I)

R ^x -[ AO ^-0-0(0)-0-( AO ² ] _m -R ² (I), where R ¹ and R ² independently represent a C ₆ -C ₃₂ hydrocarbon group,

AO ¹ and AO ² are independently C ₂ -C ₆ alkyleneoxy, and m and n are independently 2 to 100, provided that the pesticide does not include fungicides.

The term pesticide formulation generally refers to a formulation that is suitable for industrial use to control the growth of unwanted plants and/or unwanted insect attack by acting said pesticide formulation on the appropriate pests, their habitat or crop plants to be protected from pest, on the ground and/or on unwanted plants and/or on their habitat. The industrial use of pesticide formulations is usually subject to various specific legal restrictions and specific registration processes. The skilled person is well aware that other formulations, such as deodorants or pharmaceuticals, as well as cosmetics, are generally not suitable for industrial use during the control of unwanted plant growth and/or unwanted insect attack, through the action of said pesticidal formulation on relevant pests, their habitat or crop plants to be protected from the respective pest, soil and/or undesirable plants and/or their habitat.

R ¹ and R ² independently usually represent a monovalent C6-C32 aliphatic hydrocarbon group, preferably straight or branched, saturated or unsaturated C8-C20 alkyl. More preferably, R ¹ and R ² are independently straight or branched, saturated C10- _C18 alkyl. Mixtures of different hydrocarbon groups are also possible, for example mixtures of chain lengths of different lengths, and/or saturated and unsaturated hydrocarbons. In one embodiment, R ¹ and R ² are the same. In another embodiment, R ¹ and R ² are different.

Typical examples of R ¹ or R ² are straight or branched decyl, undecyl, dodecyl, tridecyl, hexadecyl, heptadecyl and octadecyl, or a mixture of the residues mentioned above. In another embodiment, examples of R ¹ or R ² are selected from C13 branched alkyl. In another embodiment, examples of R ¹ or R ² are selected from straight C12-C ₁₈ alkyl. In another embodiment, examples of R ¹ or R ² are selected from C10 branched alkyl such as 2-propylheptyl. In another embodiment, R ¹ and R ² are independently branched C10 alkyl. In a particularly preferred embodiment, R ¹ and R ² are 2-propylheptyl.

AO ¹ and AO ² independently represent usually a saturated or unsaturated, straight or branched C2-C6 alkyleneoxy group. Mixtures of different C2-C6 alkyleneoxy groups are also possible (eg, AO ¹ and AO ² are each independently a mixture of ethyleneoxy and C3-C ₆ alkyleneoxy, where a mixture of ethyleneoxy and propyleneoxy is preferred). Examples of AO ¹ or AO ² are independently ethyleneoxy, propyleneoxy, butyleneoxy, or mixtures thereof. AO ¹ or AO ² is more preferably independently ethyleneoxy, or a mixture of ethyleneoxy and propyleneoxy. In particular, AO ¹ and AO ² are ethyleneoxy.

The indices m and n are independently generally any value from 2 to 100, preferably from 2.2 to 50, more preferably from 2.5 to 20, and in particular from 3 to 13.

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The ratio of n to m is usually from 10/1 to 1/10, preferably from 3/1 to 1/3, more preferably from 2/1 to 1/2, and in particular from 1.5/1 to 1/1, 5.

In another embodiment, the alkoxylate has the formula (I) wherein R ¹ and R ² are independently straight or branched, saturated or unsaturated C ₈ -C ₂₀ alkyl, AO ¹ and AO ² are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently 2 to 50.

In another embodiment, the alkoxylate has the formula (I) wherein R ¹ and R ² are independently straight or branched, saturated or unsaturated C ₈ -C ₂₀ alkyl, AO ¹ and AO ² are ethyleneoxy, and n and m are independently from 2.5 to 20.

In another embodiment, the alkoxylate has the formula (I) wherein R ¹ and R ² are 2-propylheptyl, AO ¹ and AO ² are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently 2 to 30.

In another embodiment, the alkoxylate has the formula (I) wherein R ¹ and R ² are independently straight C ₁₂ -C ₁₈ alkyl, AO ¹ and AO ² are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently from 2 to 30.

In another embodiment, the alkoxylate has the formula (I) wherein R ¹ and R ² are independently C ₁₃ branched alkyl, AO ¹ and AO ² are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently 2 to 30 .

In one embodiment, the alkoxylate has formula (I) wherein AO ¹ and AO ² are ethyleneoxy. This variant corresponds to the alkoxylate of formula (II)

R ¹ -[O-CH ₂ -CH ₂ ] _n -OC(O)-O-[CH ₂ -CH ₂ -O] _m -R ² (II), where R ¹ , R ² , m and n are and preferred options as defined above.

The alkoxylates of formula (I) and (II) can be prepared by reacting a dialkyl carbonate (eg diethyl carbonate or dimethyl carbonate, where the latter is preferred) with an alkyl alkoxylate. Suitable alkyl alkoxylates are alkyl alkoxylates of formula (III)

R^tAObn-OH (III) where R ¹ , AO ¹ and n have the meanings as described above. The reaction can be catalyzed with alkaline catalysts such as sodium methoxide. Usually, the reaction temperature is in the range between 15 and 250°C. Various means such as vacuum can be used to remove reaction by-products (eg ethanol from diethyl carbonate). In order to obtain an alkoxylate of formula (I) or (II), the reaction product may be further purified. Preferably, the reaction product which contains an alkoxylate of formula (I) or (II) can be used without further purification as an industrial grade product. The technical grade reaction product may contain up to 40 wt.%, preferably up to 25 wt.%, and more preferably up to 15 wt.% starting materials or reaction by-products.

The composition may contain at least 0.1 wt.%, preferably at least 1 wt.% alkoxylate of formula (I). The composition according to the invention may be present as a pesticide formulation and contain from 1 to 80% by weight of the alkoxylate of formula (I), preferably from 2 to 50% by weight, and in particular from 5 to 30% by weight.

The term pesticide refers to at least one active ingredient selected from the group of insecticides and herbicides. Preferred pesticides are insecticides. Mixtures of pesticides of the two classes mentioned above can also be used. Those skilled in the art are aware of such pesticides, which can be found, for example, in the Pesticide Manual, 16th ed. (2013), The British Crop Protection Council, London. Suitable insecticides include carbamate insecticides, organophosphorus insecticides, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin nonreisotoxin analogs, benzoylureas, diacylhydrazines, METI. -acaricides, as well as insecticides such as chlorpicrin, pymetrozine, flonicamid, clofentezin, hexythiazox, ethoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acechinocil, fluacripyrim, rotenone, or their derivatives. Suitable herbicides are herbicides from the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazolilones, N-phenylphthalimides, oxadiazoles, oxazolidinediones, hydroxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoramidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinecarboxylic acid, pyrimidinecarboxylic acid acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas .

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Preferably, the pesticide is soluble in water up to 10 g/l, preferably up to 1 g/l, and in particular up to 0.5 g/l, at a temperature of 20°C.

The composition according to the invention may also be present in the form of an agrochemical formulation containing a pesticide, an alkoxylate of formula (I), and optionally an excipient. The agrochemical formulation typically contains a pesticidally effective amount of the pesticide. The term "effective amount" means an amount of a formula I compound or compounds which is sufficient to control harmful pests on or among crop plants, or to protect materials, and which does not result in substantial damage to the treated plants. This amount can vary widely and depends on various factors such as the fungal species to be controlled, the crop or material being treated, climatic conditions and the particular pesticide used.

Suitable, conventional types of agrochemical formulations are, for example, solutions, emulsions, suspensions, powders, powders, pastes, granules, tablets, capsules, and mixtures thereof. Examples of formulation types are suspensions (e.g. SC, OD, FS), emulsion concentrates (e.g. EC), dispersion concentrates (DC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC ), pastes, lozenges, wettable powders or powders (e.g. WP, SP, WS, DP, DS), tablets (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (eg LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (eg GF). These and additional formulation types are defined in the Catalog of pesticide formulation types and international coding system, Technical Monograph No. 2, 6th ed., May 2008, CropLife International.

Agrochemical formulations are often made in a known manner, such as those described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Examples of suitable excipients are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersing agents, emulsifying agents, wetting agents, co-adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion promoters, thickeners, wetting agents, repellents, attractants. , eating aids, compatibilizers, bactericides, anti-freeze agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents such as medium to high boiling point mineral oil fractions, eg kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example cyclohexanone; esters, eg lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acid; phosphonates; amines; amides, for example N-methylpyrrolidone, fatty acid dimethylamides; and their mixtures.

Suitable solid carriers or fillers are natural minerals, for example silicates, silicates, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomite, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, eg cellulose, starch; fertilizers, eg ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; vegetable products such as cereal flour, tree bark flour, wood flour, nutshell flour, and mixtures thereof.

Suitable surfactants are surface active compounds such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as an emulsifying agent, a dispersing agent, a solubilizer, a wetting agent, a penetrating agent, a protective colloid, or an adjuvant. Examples of surfactants are listed in McCutcheon's, t1.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkaline, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalenes sulfonates, dodecyl and tridecylbenzene sulfonates, naphthalenes and alkylnaphthalenes sulfonates, sulfosuccinates or sulfosuccinates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols, or fatty acid esters. Examples of phosphates are esters of phosphoric acid. Examples of carboxylates are alkyl carboxylates, as well as carboxylated alcohol or alkylphenol ethoxylates.

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Suitable non-ionic surfactants are alkoxylate surfactants, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylate surfactants are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated from 1 to 50 equivalents. For alkoxylation, ethylene oxide and/or propylene oxide, preferably ethylene oxide, can be used. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose-glucose esters, or alkyl polyglucosides. Examples of polymeric surfactants are vinylpyrrolidone homo- or copolymers, vinyl alcohols, or vinyl acetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are A-B or A-B-A type block polymers containing blocks of polyethylene oxide and polypropylene oxide, or type A-B-C containing alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable additional adjuvants are compounds which have little or no pesticidal activity per se and which improve the biological effect of the pesticide on the target. Examples are surfactants, mineral or vegetable oils, and other excipients. Additional examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, section 5.

Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and also silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable antifoam agents are silicones, long chain alcohols, and fatty acid salts.

Suitable colorants (eg red, blue, or green) are pigments with low water solubility and water-soluble paints. Examples are inorganic colorants (eg iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (eg alizarin, azo and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Examples of types of formulations and their manufacture are:

I) water-soluble concentrates (SL, LS).

10-60% by weight of the pesticide and 5-15% by weight of a wetting agent (eg alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (eg alcohols) up to 100% by weight. The active substance dissolves after dilution with water;

II) dispersion concentrates (DC).

5-25% by weight of the pesticide and 1-10% by weight of a dispersing agent (eg polyvinylpyrrolidone) are dissolved in up to and including 100% by weight of an organic solvent (eg cyclohexanone). Dilution with water gives a dispersion;

III) emulsion concentrates (EC).

15-70% by weight of the pesticide and 5-10% by weight of emulsifying agents (eg calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to and including 100% by weight of a water-insoluble organic solvent (eg aromatic hydrocarbon). Dilution with water gives an emulsion;

IV) emulsions (EW, EO, ES).

5-40% by weight of the pesticide and 1-10% by weight of emulsifying agents (eg calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40% by weight of a water-insoluble organic solvent (eg aromatic hydrocarbon). This mixture is introduced into up to and including 100 wt.% water using an emulsifier and converted into a homogeneous emulsion. Dilution with water gives an emulsion;

V) suspensions (SC, OD, FS).

In a ball mill with a stirring mechanism, 20-60 wt.% pesticide is powdered with the addition of 2-10 wt.% dispersing agents and wetting agents (for example, sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt. % thickener (e.g. xanthan gum) and up to

100 wt.% water, resulting in a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. In the case of an FS type formulation, up to 40% by weight of binder (eg polyvinyl alcohol) is added;

VI) water-dispersible granules and water-soluble granules (WG, SG).

50-80 wt.% of the pesticide is finely milled with the addition of up to 100 wt.% of dispersing agents and wetting agents (for example, sodium lignosulfonate and alcohol ethoxylate), and using technical means (for example, extrusion, reflux column, fluidized bed) is converted into dispersible in water or water-soluble granules. Dilution with water gives a stable dispersion or solution of the active ingredient;

vii) water-dispersible powders and water-soluble powders (WP, SP, WS).

50-80 wt.% of the pesticide is ground in a rotor-stator mill with the addition of 1-5 wt.% dispersing agents (for example, sodium lignosulfonate), 1-3 wt.% wetting agents (for example, alcohol ethoxylate) and up to 100 wt.% solid support, such as silica. Dilution with water gives a stable dispersion or solution of the active ingredient;

VIII) gel (GW, GF).

In an agitated ball mill, 5-25 wt.% of the pesticide is powdered with the addition of 3-10 wt. % water, resulting in a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance;

IV) microemulsion (ME).

5-20 wt.% pesticide is added to a 5-30 wt.% mixture of organic solvents (for example, fatty acid dimethylamide and cyclohexanone), 10-25 wt.% mixture of surfactants (for example, alcohol ethoxylate and arylphenol ethoxylate), and water to 100%. This mixture is stirred for 1 hour until a directly thermodynamically stable microemulsion is obtained;

IV) microcapsules (CS).

Oil phase containing 5-50 wt.% pesticide, 0-40 wt.% water-insoluble organic solvent (for example, aromatic hydrocarbon), 2-15 wt.% acrylic monomers (for example, methyl methacrylate, methacrylic acid and di- or triacrylate ) are dispersed in an aqueous solution of a protective colloid (eg polyvinyl alcohol). Radical polymerization induced by a radical initiator leads to the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase containing 5-50 wt.% pesticide, 0-40 wt.% water-insoluble organic solvent (e.g., aromatic hydrocarbon), and isocyanate monomer (e.g., diphenylmethene-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (for example, polyvinyl alcohol). The addition of a polyamine (eg, hexamethylenediamine) results in the formation of polyurea microcapsules. Monomers reach up to 1-10 wt.%. While wt.% refer to the total weight of the composition CS;

IX) dustable powders (DP, DS).

1-10 wt.% of the pesticide is finely ground and thoroughly mixed with up to and including 100 wt.% of a solid carrier, for example, finely divided kaolin;

X) granules (GR, FG).

0.5-30% by weight of the pesticide is ground finely and combined with up to and including 100% by weight of a solid carrier (eg silicate). Granulation is achieved by extrusion, spray drying or fluid bed;

XI) Ultra Low Volume (UL) liquids.

1-50% by weight of the pesticide is dissolved in up to and including 100% by weight of an organic solvent such as an aromatic hydrocarbon.

Formulation types I)=XI) may optionally contain additional excipients, such as 0.1-1 wt.% bactericides, 5-15 wt.% anti-freeze agents, 0.1-1 wt.% anti-foaming agents, and 0.1-1 wt.% colorants. A preferred type of formulation is a suspension concentrate.

Agrochemical formulations typically contain between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active ingredient (i.e. pesticide). The active ingredients are used in a purity of 90 to 100%, preferably 95 to 100% (according to NMR spectrum).

Water Soluble Concentrates (LS), Suspo Emulsions (SE), Flowable Concentrates (FS), Dry Processing Powders (DS), Water Dispersible Suspension Processing Powders (WS), Water Soluble Powders (SS), Emulsions (ES) , emulsion concentrates (EC) and gels (GF) are commonly used for the treatment of plant propagation materials, in particular seeds. These formulations, after dilution from two to ten times, give in ready-to-use preparations the concentration of the active

- 5 041806 substances, which constitute from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight. The application can be carried out before or during sowing. Methods for applying the pesticide and its formulations, respectively, to plant propagation material, in particular seeds, include such methods of application to the propagation material as dressing, coating, panning, pollination, soaking and furrow application. Preferably, the pesticide or formulations thereof, respectively, are applied to the plant propagation material in a manner where germination has not yet been induced, such as through seed dressing, panning, coating and pollination.

In the case of plant protection applications, the amounts of active ingredients used, depending on the type of desired effect, are from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha , in particular from 0.1 to 0.75 kg per ha.

In the case of treatment of plant propagation materials such as seeds, for example by pollination, coating or soaking of seeds, amounts of active ingredient are generally required which are from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably 1 to 100 g, and most preferably 5 to 100 g, per 100 kilograms of plant propagation material (preferably seeds).

When used to protect materials or stored products, the amount of active ingredient used depends on the type of surface to be applied and on the desired effect. The amounts commonly used for protecting materials are 0.001 g-2 kg, preferably 0.005 g-1 kg, of active ingredient per cubic meter of treated material.

Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and other pesticides (eg, herbicides, insecticides, fungicides, growth regulators, safeners) may be added to active ingredients or formulations containing them as a pre-additive, if necessary. , not just before use (tank mix). These substances can be mixed with the compositions according to the invention in a mass ratio of 1:100-100:1, preferably 1:10-10:1.

The concentration of the alkoxylate of formula (I) in the ready-to-use preparation (eg tank mix) is in most cases in the range which is from 0.01 to 50 g/l, preferably 0.08-10 g/l, and in particular 0 .5-8 g/l.

The water concentration in the ready-to-use formulation (eg tank mix) is in most cases at least 60% by weight, preferably at least 75% by weight, and in particular at least 90% by weight.

The tank mix typically constitutes an aqueous liquid that is ready for use (eg, by spraying) in a method of controlling phytopathogenic fungi and/or unwanted vegetation and/or unwanted attack by insects or mites and/or regulating plant growth.

The user applies the formulation according to the invention, typically using a pre-mixer, a backpack sprayer, a tank sprayer, an aerial sprayer, or an irrigation system. Typically, water, a buffer solution, and/or additional excipients are used in the agrochemical composition to bring it to the desired concentration for use and thus a ready-to-use spray solution or agrochemical composition according to the invention is obtained. Typically, 20-2000 liters, preferably 50-400 liters, of a ready-to-use spray solution are applied per hectare of agricultural usable area.

In accordance with one embodiment, the individual components of the formulation according to the invention, such as parts of a kit or parts of a double or triple mixture, can be mixed by the user in a tank sprayer, with additional excipients added if necessary.

In a further embodiment, either the individual components of the formulation according to the invention or partially premixed components, such as those containing the pesticide and adjuvant, may be mixed in the tank sprayer by the user, with additional auxiliaries and additives added as needed. In a further embodiment, either the individual components of a formulation according to the invention or partially premixed components, eg pesticide and/or adjuvant-containing components, may be used together (eg as a tank mix) or sequentially.

In addition, the present invention relates to a method for the manufacture of the composition in accordance with the invention by bringing the alkoxylate of formula (I) and the pesticide into contact, for example, by mixing. Contact can be made in the temperature range between 5-95°C. Thus, a tank mix or a pesticide formulation can be obtained.

In addition, the present invention relates to a method for controlling the growth of unwanted plants and/or unwanted attack of insects, by the action of the specified pesticide composition, on the respective pests, their habitat or crop plants, which are to be protected from the respective pest, on the ground and/ or undesirable plants and/or their habitat.

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Examples of suitable crop plants are cereals such as wheat, rye, barley, triticale, oats or rice; beets, such as sugar or fodder beets; pome crops, stone fruits and fruit and berry crops, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as oilseed rape, mustard, olives, sunflowers, coconut, cocoa, castor beans, oil palms, peanuts or soybeans; cucurbits, such as pumpkins/zucchini, cucumbers or melons; fibrous crops such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables and greens, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, pumpkin/zucchini or capsicum; laurel plants such as avocado, cinnamon or camphor; energy crops and industrial commodity crops such as corn, soybeans, wheat, oilseed rape, sugarcane or oil palms; corn; tobacco; nuts; coffee; tea; bananas; grapes (dessert grapes and grapes for winemaking); hop; grasses, such as turf; sweet grass (Stevia rebaudania)] rubber plants and forest plants, such as flowers, shrubs, deciduous trees and conifers, and propagation material, such as seeds, as well as harvested material obtained from these plants.

The term crop plants also includes plants that have been modified by breeding, mutagenesis, or recombinant methods, including biotechnological agricultural products that are on the market or under development. Meanwhile, genetically modified plants are plants whose genetic material has been modified in a way that is not possible under natural conditions as a result of crossing, mutations or natural recombination (ie, recombination of genetic material). Here, one or more genes are typically integrated into the plant's genetic material in order to improve the properties of the plant. Such recombinant modifications also include post-translational modifications of proteins, oligos or polypeptides, for example by glycosylation or binding polymers, such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.

The present invention also relates to seeds containing the composition according to the invention. Seeds can be treated for prevention with the composition according to the invention during or even before sowing or during or even before planting. For seed treatment, as a rule, water-soluble concentrates (LS), suspensions (FS), powdered preparations (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsion concentrates (EC ) and gels (GF). These formulations can be applied to seeds, neat or preferably diluted. In this case, said composition can be diluted by 2-10 times, so that in the compositions used for dressing seeds, there is from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, of the active ingredient . The application can be carried out before or during sowing. The seed treatment is known to the person skilled in the art and is carried out by pollinating, coating, pelleting, dipping or soaking the plant propagation material, the treatment being preferably carried out by pelleting, coating and pollinating or by placing in the furrow, in such a way that, for example, untimely early seed germination. It is preferred to use seed treatment suspensions. Typically, such formulations contain from 1 to 800 g/l of active ingredient, from 1 to 200 g/l of surfactants, from 0 to 200 g/l of antifreeze agents, from 0 to 400 g/l of binders, from 0 to 200 g /l dyes, and a solvent, preferably water.

In addition, the present invention relates to the use of the alkoxylate of formula (I) in accordance with the invention to improve the effectiveness of the pesticide. Generally, efficacy is improved compared to the same application of the pesticide without the alkoxylate of formula (I).

The advantages of the invention are high stability of the formulation and spray mixtures, low wind drift in the case of spray applications, good adhesion of the formulation to the surface of the treated plants, increased solubility of pesticides in the formulation, increased uptake of pesticides by the plant, or faster or enhanced pesticide action. (for example, even at a low dose of application). Other advantages are the high biodegradability of the alkoxylate; low toxicity of the alkoxylate, the ability of the alkoxylate to reduce the surface tension of aqueous formulations, or increased distribution over plant surfaces; or low harmful effect on crop plants, i.e. low phytotoxic effect.

The examples that follow illustrate the invention without implying any limitation.

Examples.

Alcohol alkoxylate A: ethoxylated (9 EO units) C ₁₂ -C ₁₈ fatty alcohol.

Alcohol alkoxylate B: ethoxylated (3 EO units) saturated iC ₁₃ alcohol, Brookfield viscosity approx. 50 mPas (23° C., 60 rpm).

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Alcohol alkoxylate B: ethoxylated (5 units EO) saturated iC ₁₃ alcohol, viscosity

Brookfield approximately 85 mPas (23°C, 60 rpm).

Alcohol alkoxylate D: ethoxylated (7 EO units) saturated iC ₁₃ alcohol, viscosity

Brookfield approximately 100 mPas (23°C, 60 rpm).

Alcohol alkoxylate D: ethoxylated (10 EO units) saturated iC ₁₃ alcohol, Brookfield viscosity approx. 30 mPas (60° C., 60 rpm).

Alcohol alkoxylate E: ethoxylated (12 EO units) saturated iC ₁₃ alcohol, Brookfield viscosity approx. 40 mPas (60° C., 60 rpm).

Alcohol alkoxylate E: ethoxylated (3 EO units) C ₁₂ -C ₁₈ fatty alcohol, pour point <13°C.

Alcohol alkoxylate G: ethoxylated (5 EO units) C ₁₂ -C ₁₈ fatty alcohol, solidification point approx. 12°C.

Alcohol alkoxylate H: ethoxylated (7 EO units) C ₁₂ -C ₁₈ fatty alcohol, solidification point approx. 15°C.

Alcohol alkoxylate I: ethoxylated (3 EO units) 2-propylheptanol, HLB approximately 9.

Alcohol alkoxylate Y: ethoxylated (4 EO units) 2-propylheptanol, HLB approx. 10.5.

Alcohol alkoxylate K: ethoxylated (6 units EO) 2-propylheptanol, HLB approximately 12.5.

Examples 1-15. Obtaining an alkoxylate.

199.5 g of alcohol A alkoxylate (0.33 mol) and diethyl carbonate or dimethyl carbonate (0.23 mol) were mixed with 0.59 g of sodium methoxide (30% in methanol) and heated to 80° C. with stirring. The temperature was raised to 140°C, and the resulting ethanol was distilled off. When the ethanol was no longer distilled off, a vacuum of 1 mbar was applied to remove additional volatiles. Finally, the formulation was cooled to room temperature and filtered. 175 g of product was obtained as a yellowish product. Alkoxylates of alcohols B-K reacted with diethyl carbonate, respectively, as a result of which an alkoxylate of formula (I) was obtained in accordance with the invention (Table 1, column Starting product shows alkoxylates of alcohols A-K.

Table 1 Product Features

Etc. original product SZ (mg KOH/g) VZ (mg KOH/g) OHZ (mg KOH/g) Water (%) Density (20 °C; g/cm ³ ) Refraction (YuoO) 1 B 0.16 69 29.2 0.28 0.9552 1.4561 2 IN 0.12 59.2 38.6 0.13 0.9826 1.4571 3 G 0.12 42.9 33.9 0.17 1.0002 1.4601 4 Yo 0D1 70.1 32.6 0.15 0.9512 1.4548 5 AND oh and 51.1 35.8 0.15 0.9789 1.4573 6 3 0.18 41.8 32.2 0.18 0.9995 1.4595 7 AND OD 99.5 8.8 0.13 0.973 1.4512 8 TO 0.19 81.4 12.8 0.14 0.9829 1.4526 9 Y 0.18 70 18.7 0.18 1.0071 1.4565 10 3 0.21 49.5 18.1 0.14 1.0037 1.4598 AND d 0.19 71.9 15.8 0.14 1.0254 1.4628 12 d 0.12 58.2 0.38 0.09 1.0269 1.4611 13 A 0.17 41.9 13.7 0.5 1.0168 1.4641 14 E 0.13 32.8 I,7 0.14 1.0418 1.4641 15 3 0.27 55 1.7 0.21 1.0079 1.46

SZ means total acid number;

VZ is the saponification number;

OHZ means hydroxyl number).

Example 16 Enhanced biological activity.

The biological effect was evaluated in a growing house on wheat (Kanzler spp.) that had been infected with Puccinia triticina in the two-leaf phase and incubated for three days at high humidity. The plants were sprayed (spray volume 200 l/ha) with a formulation containing 50 ppm. (10 g/ha) epoxiconazole and 100 ppm. (20 g/ha) of the respective adjuvant samples from Examples 1-15. in the comparative example, no adjuvant was added. Plants were further grown for ten days at 20-24°C and 60-90% relative humidity. Finally, the percentage of infected leaf area (pustules) was visually assessed. Each value was based on three repetitions. The results are summarized in table. 2. For comparison, the raw material alcohol alkoxylate E, which was used to make the product of Example 4, was examined.

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table 2

Sample from Example Infected leaf area -a) b) 75 Alcohol alkoxylate Yo ^a} eleven 4 8

a) comparative example;

b) without adjuvant.

Example 17 Enhanced biological activity.

Biological performance was evaluated in a growing house as described in Example 16 using a reduced pesticide application rate of 2.5 g/ha. The results are summarized in table. 3. For comparison, the raw material alcohol alkoxylate E, which was used to make the product of Example 4, was examined.

Table 3

Sample from Example Infected leaf area - A) 75 Alcohol alkoxylate Y ^a) 33 4 24

a) comparative example without adjuvant.

Example 18 Surface Tension

Physical measurements were carried out using a 1 g/l solution or dispersion of the samples from Examples 1-15 in deionized water. Static or equilibrium surface tension is a characteristic value of activity at the interface of the formulation in the spray solution. Below the critical micellization concentration (CMC), the static surface tension depends on the concentration of surfactant ingredients in the formulation, while above the CMC, the static surface tension remains constant. Measurements were made using a Kruess K 100 tensiometer using the Wilhelmy plate wetting method. During measurements, the bottom line of a vertically suspended platinum plate was wetted with the liquid to be analyzed. The force with which the plate enters the liquid was measured, which can be converted into the surface tension of the liquid, expressed in mN/m. 40 ml of the resulting spray solution was filled into Teflon crucibles in the apparatus, and the surface tension was determined. The static surface tension was calculated as soon as five consecutive measurement points corresponded to a value of 0.1 mN/m. The results are summarized in table. 4.

_______________________________________Table 4

Sample from Example Based alcohol alkoxylate Surface tension [mN/m] 6 3 thirty 5 AND 33 4 Yo 29 9 TO 29 8 AND 28 7 AND 28 3 G thirty 2 IN 29 1 B 28

Example 19 Increased Absorption Intensity.

Wheat (Triticum aestivum cv. Melon) plants were grown in a grow house for 6 weeks until the growth and development phase of BBCH 39. Plants were transferred to an automatic laboratory sprayer and sprayed with 125 g/ha epoxiconazole, 125 g/ha fluxapiroxad, and 250 g/ha of the respective adjuvant according to the following parameters.

Water quantity: 200 l/ha.

Atomizer type: air injector, ID 120 02 (Lechler, Germany).

Speed: 1.4 m/s.

Pressure: 3.33 bar.

After spraying, the plants were again grown in the growing house under ambient conditions. After 8 days, samples of 10-15 treated leaves were cut and weighed.

The leaves were cut into small pieces, transferred to glass bottles and washed using 50% methanol in demineralized water as a wash medium for 5 minutes. Then, the washing medium was separated from the leaves. The leaves were again washed using wash medium for 5 minutes. Both wash media were combined and diluted for analysis.

Finally, the leaves were transferred to a vessel containing extraction medium (75% methanol, 20% water and 5% HCl) and homogenized using a Polytron PT 6100 disperser (Kinematica, Switzerland) for 2 min. 10 ml of the extract was centrifuged at 4000 rpm for 5 minutes. 2 ml of the supernatant was treated with 2 ml of NaOH (0.2 mol/l) and 5 ml of cyclohexane, and stirred for 30 min, and then centrifuged. 1 ml phase

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Claims (14)

cyclohexane was transferred into a glass vessel and dried (Liebisch N2 Evaporator, Germany). The residue was dissolved in methanol/water 50:50 and analyzed by HPLC-MS/MS. An Agilent 1100 series liquid chromatograph was used coupled to an Applied Biosystems API 3000 triple lens quadrupole mass spectrometer equipped with a sputtered electroionization source. The mass spectrometer operated in positive ion MS/MS mode with multiple reaction monitoring (MRM) using two transitions per analyte under optimal conditions. In addition, plants that were not sprayed were treated in the same way to see if they were infected. Standard active ingredient was added to the leaves of plants that were not sprayed to determine the recovery of the active ingredient during the washing and extraction steps. According to the degree of extraction, the set values of the samples were corrected. The results were summarized in table. 5. For comparison, the starting material of alcohol alkoxylate Y, which was used to make the product of Example 4, was examined. For another comparison, the starting material of alcohol alkoxylate Y, which was used to make the product of Example 5, was examined. The data showed that the absorption rate of epoxiconazole and fluxapiroxad was increased with the use of adjuvants in accordance with the invention. Table 5. Absorption intensity Sample Example Epoxiconazole absorption rate [%] Absorption rate of fluxapiroxade [%] - a), b) 8 4 Alcohol alkoxylate E ^a) 36 23 4 62 38 Alcohol alkoxylate G ^a) 35 21 5 56 39 a) a comparative example; b) without any adjuvant. Example 20 Enhanced biological activity. The biological effect was evaluated in a growing house on wheat (Kanzler spp.) that had been infected with Puccinia triticina in the two-leaf phase and incubated for three days at high humidity. The plants were sprayed (spray volume 200 l/ha) with a formulation containing 50 ppm. (10 g/ha) epoxiconazole and 100 ppm. (20 g/ha) of the respective adjuvant samples (column application dose 10 g/ha). Alternatively, an application dose was investigated which was 50 g/ha epoxiconazole and 100 g/ha adjuvant (50 g/ha application dose column). In the comparative example, no adjuvant was added. The plants were further grown for ten days at a temperature of 20-24°C and a relative humidity of 60-90%. Finally, the percentage of infected leaf area (pustules) was visually assessed. Each value was based on three repetitions. The results are summarized in table. 6. Table 6 Sample from Example Infected leaf area application dose 50 g/ha Infected leaf area application dose 10 g/ha - A) 75 75 15 6 6 5 6 6 4 7 7 3 18 18 a) comparative example without adjuvant. CLAIM 1. Pesticide composition containing a pesticide selected from a herbicide and an insecticide and an alkoxylate of formula (I) R ¹ -[AO ¹ ]nOC(O)-O-[AO ² ]mR ² (I), where R ¹ and R ² independently represent Cb-Cs2-hydrocarbon group, AO ¹ and AO ² independently represent a Cr-C6-alkyleneoxy group, and nm independently represents a value from 2 to 100, provided that the pesticide does not include fungicides. 2. The pesticide formulation according to claim 1, wherein R ¹ and R ² are independently straight or branched, saturated or unsaturated C ₈ -C ₂ o-alkyl. - 10041806 3. Pesticide composition according to π. 1 or 2, where pit is independently a value from 2.5 to 20. 4. A pesticide formulation according to any one of claims 1 to 3, wherein AO ¹ and AO ² are independently ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy. 5. A pesticidal composition according to any one of claims 1 to 4, wherein R ¹ and R ² are independently straight or branched, saturated C^-C^-alkyl. 6. Pesticide composition according to any one of claims 1 to 5, wherein the weight ratio of pesticide to alkoxylate of formula (I) is from 4:1 to 1:10, preferably from 2:1 to 1 A. 7. Pesticide composition according to any one of claims 1 to 6, wherein the ratio of η to m is from 10/1 to 1/10, preferably from 3/1 to 1/3. 8. The pesticide formulation according to any one of claims 1 to 7, wherein R ¹ and R ² are independently straight or branched, saturated or unsaturated C8-C ₂ o-alkyl, AO ¹ and AO ² are independently ethyleneoxy or ethyleneoxy and propyleneoxy, and η and m are independently a value from 2 to 50. 9. Pesticide composition according to any one of claims 1 to 8, where the alkoxylate has the formula (II) R ¹ -[O-CH ₂ -CH ₂ ] _n -OC(O)-O-[CH ₂ -CH ₂ -O] _m -R ² (II), where R ¹ , R ² , type are as defined in any of paragraphs.1-8. 10. A pesticide formulation according to any one of claims 1 to 9, wherein R ¹ and R ² are independently straight or branched, saturated or unsaturated Sv-C ₂ o-alkyl, AO ¹ and AO ² are ethyleneoxy, and η and m independently represent a value from 2.5 to 20. 11. Method for the manufacture of a pesticide composition according to any one of claims 1 to 10 by bringing into contact a pesticide and an alkoxylate of formula (I). 12. A method of controlling unwanted plant growth and/or unwanted insect attack by acting the pesticidal composition according to any one of claims 1 to 10 on the respective pests, their habitat or crop plants to be protected from the respective pest, on the soil and /or undesirable plants and/or their habitat. 13. Seeds containing the pesticidal composition according to any one of claims 1 to 10. 14. The use of an alkoxylate of formula (I) according to any one of claims 1 to 10 to improve the effectiveness of a pesticide in a pesticide formulation containing a pesticide selected from a herbicide and an insecticide, provided that the pesticide does not include fungicides. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2 -