CONCENTRATED LIQUID COMPOSITIONS BASED ON N-PHOSPHONOMETHYLGLYCINE.

Abstract

Compositions concentrées contenant de la N-phosphonométhylglycine et / ou l'un de ses dérivés sous forme de compositions liquides constituées de suspensions liquides en milieu solvant organique, contenant: a) de la N-phosphonométhylglycine et / ou l'un de ses dérivés ayant une solubilité propre dans l'eau supérieur à 5 g / l, cette N-phosphonométhylglycine et / ou son dérivé se trouvant dans les compositions à raison d'au moins 100 g / l d'équivalent glyphosate, une partie au moins de cette N-phosphonométhylglycine ou de ses dérivés étant sous forme insoluble dans le milieu considéré, b) un tensioactif à caractère activateur et ayant pour formule (CF DESSIN DANS BOPI) dans laquelle R est une chaîne hydrocarbonée linéaire ou ramifiée, alkyle ou alkényle, (8 à 22 atomes de carbone), A représente un groupe alkylène, n + n' est compris entre 2 et 41 de préférence entre 20 et 25. R1 est H ou acyle.

Description

The present invention relates to new concentrated formulations based on N-phosphonomethylglycine or compounds with an N-phosphonomethylglycyl group. N-phosphonomethylglycine (sometimes called glyphosate), as well as similar compounds, their herbicidal properties and formulations containing them, are described in particular in the patent US 3,799,758. Although many water-soluble or water-insoluble derivatives of glyphosate are known, in fact water-soluble derivatives are generally preferred, and that is why N-phosphonomethylglycine salts have generally been developed or marketed, especially isopropylammonium salt. More recently (European patent application no. 290416), efforts have been made to develop concentrates based on N-phosphonomethylglycine salts. These concentrates may contain N-phosphonomethylglycine in its acidic form, but must in any case contain N-phosphonomethylglycine and / or its derivatives in soluble or solubilized forms. These concentrates are solutions characterized by the presence of an activator, which is an alkoxylated amine of a particular type. This alkoxylated amine must have no more than 12 alkoxy groups per molecule, and it must act as a surfactant and enhance the herbicidal activity of the N-phosphonomethylglycine derivatives. It can be used in smaller quantities than the known surfactants in existing N-phosphonomethylglycine formulations, at least for the preparation of concentrates intended for outdoor application as diluted sprays at a rate of 100 to 600 L / ha. Formulations including a tetraaluminum salt and N-phosphonomethylglycine, practically insoluble in water, and a special type of surfactant. One consequence of this insolubility of the active ingredient is that when the concentrate is diluted in water to obtain the final spray solution, this solution is not in the form of a perfect solution, which hinders application and the achievement of satisfactory efficacy. However, those skilled in the art are not inclined to apply the formulations of this patent to active ingredients with higher solubility, because experience shows that preparing concentrated suspensions from partially soluble active ingredients encounters significant difficulties due to the tendency of concentrated suspensions to clump.One explanation for these difficulties and this clumping is that there is a marked tendency for crystal growth in the continuous (aqueous) phase of the suspensions, this growth being able to develop extremely to the point of clumping. One object of the present invention is to provide compositions based on N-phosphonomethylglycine or its derivatives having a concentration of active material significantly higher than similar compositions known in the prior art. Another object of the present invention is to provide compositions based on Nphosphonomethylglycine or its derivatives which may also include adjuvants, such as ammonium mineral salts, at concentrations significantly higher than those of similar compositions known in the prior art. Another objective of the present invention is to provide concentrates based on N-phosphonomethylglycine or its derivatives giving rise to diluted slurries having good herbicidal activity. Another object of the present invention is to provide concentrated compositions based on N-phosphonomethylglycine or its derivatives, and further comprising one or more surfactants with activating action, that is to say, having an action that promotes the biological activity of the active ingredient, and especially its herbicidal activity Another objective of the present invention is to provide concentrated compositions, based on N-phosphonomethylglycine or its derivatives, and having favorable properties, such as good and rapid dispersibility in water. Another objective of the present invention is to provide concentrated compositions, based on N-phosphonomethylglycine or its derivatives, and having favorable properties, such as good fluidity at low temperature Another object of the present invention is to provide concentrated compositions, based on N-phosphonomethylglycine or its derivatives, and having favorable properties, such as a low tendency to produce foam, which allows the use of smaller quantities of antifoaming agent. Another object of the present invention is to provide concentrated compositions, or formulations (also called concentrates) based on N-phosphonomethylglycine, and especially on simple N-phosphonomethylglycine which is poorly soluble in water. Another object of the present invention is to provide N-phosphonomethylglycine-based compositions having the aforementioned advantages, these compositions further comprising one or more other herbicides. It has now been found that these goals can be achieved, in whole or in part, by means of the compositions according to the invention. In what follows, percentages are, unless otherwise specified, weight / volume percentages. Furthermore, the equivalent glyphosate is defined as the quantity of product corresponding to the quantity of product if all the N-phosphonomethylglycine derivative were in the form of ordinary N-phosphonomethylglycine. These compositions are liquid compositions consisting of (concentrated) suspensions in an organic, or possibly hydro-organic, solvent medium, containing: a) N-phosphonomethylglycine and / or one of its derivatives having an intrinsic solubility in water greater than 5 g / L, preferably greater than 9 g / L, this N-phosphonomethylglycine and / or its derivative being present in the compositions at a concentration of at least 100 g / L glyphosate equivalent, at least a portion of this N-phosphonomethylglycine or its derivatives being insoluble in the medium considered (the insolubility arises in particular from the fact that the quantity of N-phosphonomethylglycine and / or its derivative exceeds the solubility limit in the medium); b) a surfactant with activating properties and having the following formula EMI5.1 in which R is a linear or branched hydrocarbon chain, alkyl or alkenyl, having from 8 to 22 carbon atoms A represents an alkylene group, preferably ethylene or propylene n and n' are integers such that n + n' is between 2 and 40 preferably between 16 and 30, and even more preferably between 20 and 25. R1 is the hydrogen atom or an acyl radical such as formyl, acetyl, propanoyl (i.e. CH3 CH2- CO), benzoyl. Of course, this single surfactant-activator can be replaced by a mixture of surfactants in which, on average, R, n and n' meet the definitions given above. The active herbicidal ingredient used in the invention is therefore N-phosphonomethylglycine and / or one of its derivatives having a solubility in water greater than 5 g / L, preferably greater than 9 g / L. The numerous derivatives of N-phosphonomethylglycine known per se, particularly salts, can be used as derivatives, either individually or in mixtures. Among the most suitable derivatives are sodium, potassium, mineral or organic ammonium salts, particularly isopropylammonium salts, as well as sulfonium salts; N-methyl-N-(methylsulfonyl)-N-0N'-(phosphonomethyl)glycylamine; aluminum salts are not included in the invention. Of course, the use of these products must comply with the percentage and solubility requirements specified elsewhere. Advantageously, the present invention relates to concentrated compositions as described above and further comprising one and / or the other of the following characteristics: a) N-phosphonomethylglycine or its derivative is in an amount exceeding the solubility limit in the medium considered, preferably between 120 and 250 g / l, and even more preferably between 160 and 220 g / l; the proportion of undissolved N-phosphonomethylglycine derivative is greater than 30%, preferably greater than 75X. b) N-phosphonomethylglycine, or its derivative, which is insoluble, is in the form of solid particles with a diameter of less than 30 microns, preferably between 1 and 20 microns. c) the concentrated composition includes an ammonium salt (NH4+) such as nitrate, phosphate, sulfamate, thiocyanate or preferably sulfate, at a rate of 100 to 500 g / l, preferably 200 to 350 g / l. d) the concentrated compositions are intended to be diluted by farmers in containers containing water so that these diluted mixtures can be spread at a rate of 100 to 600 l / ha, the active material being applied at a rate of 0.125 to 1.5 kg / ha. e) the weight ratio e,uivaIen t gI hosate The surfactant (activator) is between 0.5 and 6, preferably between 0.6 and 2. This relatively high quantity of surfactant relates to this surfactant with the character of a biological activator / herbicide, it being understood that the compositions according to the invention may also contain, as will be specified below, all kinds of other components, and in particular surfactants (or surfactants) of the most diverse natures with wetting, dispersing or emulsifying character; these surfactants are then used at doses much lower than the dose of the activator. (f) The solvent is an organic solvent, preferably miscible with water, containing up to 50% water, preferably less than 30%, said solvent being such that N-phosphonomethylglycine is sparingly soluble in it, i.e. soluble at less than 80 g / l, preferably less than 40 g / l The concentrated suspensions according to the invention are prepared in such a way as to obtain a stable, free-flowing product that does not settle (fine grinding). They typically contain 10 to 75% active ingredients (herbicides), 0.5 to 40% activating surfactant(s), 10 to 50% ammonium salt (adjuvant), 0.1 to 10% ordinary surfactant(s) (i.e., those with dispersing, wetting, and / or emulsifying properties), 0 to 30% suitable additives such as antifoams, corrosion inhibitors, protective colloids, thickeners, sequestrants, thixotropic or pseudoplastic agents, stabilizers, penetrating agents, and adhesives, and, as a carrier, an organic liquid in which the active ingredient is sparingly soluble or insoluble. Certain organic solids or mineral salts may be dissolved or suspended in the carrier to help prevent sedimentation or as antifreeze.More generally, the compounds used in the invention can be associated with all solid or liquid additives corresponding to the usual formulation techniques. In addition to N-phosphonomethylglycine and / or its derivatives, the compositions implemented in the invention may contain other known active substances with herbicidal properties or plant growth regulating properties. Examples of herbicidal materials that can be mixed with glyphosate derivatives in compositions according to the invention include acifluorfen, aclonifen, bifenox, diflufenican, asulam, triazines (in particular simazine and atrazine), diuron and oxadiazon, hormone or phenoxy herbicides, in particular 2,4-D, 2,4-DB, MCPP, hydroxybenzonitriles (in particular bromoxynil and ioxynil), imidazolinones (in particular imazaquin and imazapur), and sulfonylureas (in particular chlorsulfuron and metsulfuron). The preceding names are standardized names for herbicides. These herbicides are most often used at a rate of 1 to 400 parts by weight per 100 parts of glyphosate or glyphosate equivalent. Using the term glyphosate equivalent reduces the calculation of parts to the assumption that all glyphosate derivatives were in the form of N-phosphonomethylglycine. More specifically, when using herbicide active ingredients other than glyphosate and mixed with glyphosate, the following proportions are generally used for the weight ratio rp glyphosate or glyphosate equivalent (rp is equal to other herbicide glyphosate + acifluorfen: 4 S rp < 9 100 100 glyphosate + diuron or oxadiazon: 2 < rp # 4 glyphosate + aclonifen: 1 S rp S 10 3 3 glyphosate + bifenox: 1 S rp S 1 3 glyphosate + diflufenican: 2 # rp < 20 glyphosate + asulam: 1 # rp # 1 4 glyphosate + phenoxy: 2 S rp # 4 3 glyphosate + hydroxybenzonitrie: 1 # rp # 10 glyphosate + triazine: < rp # 1 3 glyphosate + imidazolinone: 1 < rp # 4 glyphosate + sulfonylurea: 100 # rp < 100 6 As previously stated, the concentrated suspensions according to the invention comprise an organic solvent (or sometimes called a carrier). This solvent is an organic or mineral material, natural or synthetic, with which the active ingredient(s) are combined to facilitate their application to the plant or soil. This solvent is therefore generally inert and acceptable in agriculture, particularly on the treated plant. In the present invention, the solvent may thus be an organic liquid such as, for example, esters, particularly methyl glycol acetate; ketones, particularly cyclohexanone and isophorone; petroleum fractions; aromatic hydrocarbons, particularly xylenes, or paraffinic hydrocarbons; aliphatic or aromatic chlorinated hydrocarbons, particularly chlorobenzenes; glycols; liquid oligoglycols or polyglycols, i.e., low molecular weight; and possibly esterified vegetable oils. As previously stated, the concentrated compositions according to the invention may contain one or more surfactants, in addition to the activator-like surfactant defined above. As a surfactant, one may use an emulsifying, dispersing or wetting agent of the ionic or non-ionic type or a mixture of such surfactants. Examples include salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of esters of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of alcohols or polyoxyethylated phenols, esters of fatty acids and polyols, and sulfate, sulfonate and phosphate derivatives of the preceding compounds. The following examples, given by way of non-limiting purpose, illustrate the invention, in particular the concentrated suspensions according to the invention and their use, and show how this invention can be implemented. EXAMPLE 1 * N-phosphonomethylglycine (acid) 200 g / l * ammonium sulfate (adjuvant) 200 g / l * surfactant (activator) defined below 200 g / l * dispersants / wetting agents tris(phenylethyl)phenol phosphate polyethoxylated 20 g / l Ammonium dodecylbenzene sulfonate 10 g / l * organopolysiloxane oil (antifoam) 2 g / l * bentonite (thixotropic agent) 2 g / l * polyvinyl alcohol (protective colloid) 8 g / l * solvents: propylene glycol 300 g / l water 250 g / l The surfactant used in this example was a product with the formula EMI11.1 This mixture is ground in a ball mill to obtain a concentrated microsuspension in which 73% of the N-phosphonomethylglycine is suspended as particles with a size between 5 and 20 microns. A fraction of this concentrated suspension is treated by centrifugation; after analysis of the liquid phase, 27 g / l of N-phosphonomethylglycine is found in this liquid phase. This concentrated composition retains its physicochemical properties. a) after a one-month stay at 50°C, as well as b) after a stay of one month divided into eight periods of equal duration, four at 35 C and four at -10 C alternately. A concentrated composition such as that prepared in this example is then diluted in water at a ratio of one liter of concentrate to 100 liters of water. This produces, almost instantly, a diluted and homogeneous spray solution which is applied at a rate of 250 g / ha to the following weeds: Portulaca oleracea, Centauria cyanus, Sinapis arvensis, Panicum trichoides, and Abutilon theophrasti. At an active ingredient dose of 500 g / ha, the above weeds are controlled at respective rates of 95%, 100%, 98%, 100%, and 100%. EXAMPLE 2 * N-phosphonomethylglycine (acid) 200 g / l * ammonium sulfate (adjuvant) 200 g / l * surfactant (activator) used in example 1: 200 g / l * dispersants / wetting agents tris(phenylethyl)phenol phosphate polyethoxylated 20 g / l Ammonium dodecylbenzene sulfonate 10 g / l * organopolysiloxane oil (antifoam) 2 g / l * polyvinyl alcohol (protective colloid) 2 g / l * bentonite (thixotropic agent) 8 g / l * solvent polyethylene glycol (molecular weight = 400 ) 552 g / l This mixture is ground as in example 1 and exhibits the same stability characteristics as the concentrated composition of example 1. EXAMPLE 3 * N-phosphonomethylglycine (acid) 125 g / l * Oxadiazon 125 g / l * surfactant used in example 1: 125 g / l * (NH4)2SO4 125 g / l * dispersant / wetting agent tris(phenylethyl)phenol phosphate polyethoxylated 20 g / l ammonium dodecylbenzene sulfonate 10 g / l Polyethoxylated dodecanol (30 EO) 50 g / l * organopolysiloxane oil 2 g / l * bentonite (thixotropic agent) 2 g / l * polyvinyl alcohol (protective colloid) 8 g / l * solvent: polyethylene glycol (MW = 400) 410 g / l This mixture is ground as in example 1 and exhibits the same stability characteristics as the concentrated composition of example 1. EXAMPLE 4 * N-phosphonomethylglycine (acid) 125 g / l * Aclonifen 250 g / l * surfactant used in example 1: 125 g / l * (NH4)2SO4 125 g / l * dispersant / wetting agent tris(phenylethyl)phenol phosphate Polyethoxylated 30 g / l * Propylene glycol 270 g / l * H2O 175 g / l This mixture is ground as in example 1 and exhibits the same stability characteristics as the concentrated composition of example 1. EXAMPLE 5 * N-phosphonomethylglycine (acid) 200 g / l * Chlorsulfuron 2 g / l * surfactant used in example 1 200 g / l * (NH4)2SO4 200 g / l * dispersant / wetting agent tris(phenylethyl)phenol polyethoxylated phosphate 14 g / l Tetraethoxylated dodecanol 14 g / l Decanol hexaethoxylated 40 g / l * Attapulgite (thixotropic agent) 8 g / l * Solvents in sufficient quantity for 1 1 aromatic hydrocarbons, petroleum distillation fraction containing Cs to Cl compounds. This mixture is ground as in example 1 and exhibits the same stability characteristics as the concentrated composition of example 1. This concentrated composition is diluted to apply 750 g / ha of active ingredient and 300 l / ha of diluted spray solution to land infested with weeds. The following destruction rates were observed on the treated weeds: 99.7% (centauria cyanus), 97.5% (chrysanthemum), 80% (galium aparine), 85% (sinapis alba), 92.5% (sinapis arvensis), 92.5% (stellaria media), 93.5% (agrotis tenuis), 96.5% (alopecurus myosuroides), 98.5% (avena fatua), 97.6% (lolium multiflorum), 97.6% (phalaris canariensis), 82.5% (poa annua).

Claims

DEMANDS 1) Concentrated compositions containing N-phosphonomethylglycine and / or one of its derivatives, characterized in that they are liquid compositions consisting of suspensions in an organic, or possibly hydro-organic, solvent medium, containing: a) N-phosphonomethylglycine and / or one of its derivatives having an intrinsic solubility in water greater than 5 g / l, preferably greater than 9 g / l, this N-phosphonomethylglycine and / or its derivative being present in the compositions at a concentration of at least 100 g / l glyphosate equivalent, at least a portion of this N-phosphonomethylglycine or its derivatives being insoluble in the medium considered; b) a surfactant with activating properties and having the formula EMI15.1 in which R is a linear or branched hydrocarbon chain, alkyl or alkenyl, having from 8 to 22 carbon atoms A represents an alkylene group, preferably ethylene or propylene n and n' are integers such that n + n' is between 2 and 40. R1 is the hydrogen atom or an acyl radical such as formyl, acetyl, propanoyl (i.e., CH- CH2- CO), benzoyl. 2) Compositions according to claim 1 characterized in that A is an ethylene or propylene group, and / or n + n' is between 16 and 30, preferably between 20 and 25. 3) Compositions according to any one of claims 1 or 2 characterized in that the Nphosphonomethylglycine derivative is selected from the group consisting of sodium, potassium, mineral or organic ammonium salts, in particular isopropylammonium salts, as well as sulfonium salts, taken alone or in mixture. 4) Compositions according to any one of claims 1 to 3 characterized in that the N-phosphonomethylglycine or its derivative is in an amount exceeding the solubility limit in the medium considered, preferably between 120 and 250 g / l. 5) Compositions according to claim 4 characterized in that the N-phosphonomethylglycine or its derivative is in an amount between 160 and 220 g / l. 6) Compositions according to any one of claims 4 or 5 characterized in that the proportion of undissolved N-phosphonomethylglycine derivative is greater than 30%, preferably greater than 75%. 7) Compositions according to any one of claims 1 to 6 characterized in that the N-phosphonomethylglycine, or its derivative, which is insoluble, is in the form of solid particles of diameter less than 30 microns, preferably between 1 and 20 microns. 8) Compositions according to any one of claims 1 to 7 characterized in that they comprise an adjuvant such as an ammonium salt, this salt being in particular a nitrate, or a phosphate, or a sulfamate, or a thiocyanate or a sulfate, 9) Compositions according to claim 8 characterized in that they comprise an adjuvant at a rate of 100 to 500 g / l, preferably 200 to 350 g / l. 10) Compositions according to any one of claims 1 to 9, characterized in that they are intended to be diluted with water so as to be spread at a rate of 100 to 600 L / ha, the active ingredient being applied at a rate of 0.125 to 1.5 kg / ha