AU2007306326B2

AU2007306326B2 - Solvent composition containing at least two solvents, and phytosanitary formulation containing said composition and an active ingredient

Info

Publication number: AU2007306326B2
Application number: AU2007306326A
Authority: AU
Inventors: Valerio Bramati; Wagner Lourenco
Original assignee: Specialty Operations France SAS
Current assignee: Specialty Operations France SAS
Priority date: 2006-10-13
Filing date: 2007-10-11
Publication date: 2010-06-03
Anticipated expiration: 2027-10-11
Also published as: EP2076119A1; DE602007004874D1; ATE457638T1; ES2340549T3; AU2007306326A1; BRPI0719277A2; PT2076119E; EP2076119B2; EP2076119B1; WO2008043807A1; BRPI0719277B1

Abstract

The invention relates to a concentrated phytosanitary formulation containing an active ingredient. The composition includes two solvents. It is stable and can be readily used by farmers. The present invention also relates to a solvent composition useful and essentially preferred for preparing the phytosanitary formulation.

Description

-1 SOLVENT COMPOSITION COMPRISING AT LEAST TWO SOLVENTS, AND PLANT-PROTECTION FORMULATION COMPRISING SAID SOLVENT COMPOSITION AND AN ACTIVE COMPOUND The present invention relates to a concentrated plant 5 protection formulation comprising an active compound. The composition comprises at least two solvents. It is stable, and is easy to use by farmers. The present invention also relates to a solvent composition that is useful and preferred especially for using the plant-protection 10 formulation. Agriculture uses many active materials such as fertilizers or pesticides, for example insecticides, herbicides or fungicides. They are referred to as active plant protection products (or active materials) . Active plant 15 protection products are generally products in pure or highly concentrated form. They must be used on farms at low concentrations. To this end, they are generally formulated with other ingredients so as to allow easy weight dilution by the farmer. These are referred to as 20 plant-protection formulations. The dilution effected by the farmer is generally performed by mixing the plant protection formulation with water. Thus, plant-protection formulations should allow easy weight dilution by the farmer, in order to obtain a product 25 in which the plant-protection product is correctly dispersed, for example in the form of a solution, emulsion, suspension or suspenso-emulsion. Plant-protection formulations thus allow the transportation of a plant protection product in relatively concentrated form, easy 30 packaging and/or easy handling for the final user. Different types of plant-protection formulation may be used according to the different plant-protection products. Mention is 2 made, for example, of emulsifiable concentrates (EC), concentrated emulsions (emulsion in water, EW), microemulsions (ME), wettable powders (WP) and water dispersible granules (WDG). The formulations that it is 5 possible to use depend on the physical form of the plant-protection product (for example solid or liquid) and on its physicochemical properties in the presence of other compounds such as water or solvents. 10 After weight dilution by the farmer, for example by mixing with water, the plant-protection product may be in various physical forms: solution, dispersion of solid particles, dispersion of droplets of the product, droplets of solvent in which the product is dissolved, 15 etc. Plant-protection formulations generally comprise compounds that enable these physical forms to be obtained. They may be, for example, surfactants, solvents, mineral supports and/or dispersants. Quite often, these compounds do not have any active nature, 20 but intermediary nature that aids formulation. It is thus often desired to limit their amounts in order to limit the costs and/or any harm to the environment. Plant-protection formulations may especially be in liquid form or in solid form. 25 For practical reasons (for example for reasons of ease of handling and/or transportation), it may occasionally be preferred to use plant-protection formulations in solid form, and occasionally to use formulations in 30 liquid form. In order to prepare plant-protection formulations of solid active plant-protection products, it is known practice to dissolve the product in a solvent. The 35 plant-protection formulation thus comprises a solution of the product in the solvent. The formulation may be in solid form, for example in the form of a wettable 3 powder (WP) in which the solution soaks a mineral support, for example kaolin and/or silica. Alternatively, the formulation may be in liquid form, for example in the form of an emulsifiable concentrate 5 (EC) having a single clear liquid phase comprising the solvent and the product in solution, which can form an emulsion by adding water, without stirring or with gentle stirring. It may also be in the form of a cloudy concentrated emulsion (CE), whose water-dispersed phase 10 comprises the solvent and the product dissolved in the solvent. It may also be in the form of a clear microemulsion (ME), whose water-dispersed phase comprises the solvent and the product dissolved in the solvent. 15 Certain solid plant-protection active agents are often difficult to formulate. For example, tebuconazole is a particularly effective fungicide and is widely used, especially for soybean crops. For certain plant 20 protection active agents, it is difficult to produce concentrated formulations that are easy for the farmer to dilute, stable and free of substantial drawbacks (real or perceived) with regard to safety, toxicity and/or ecotoxicity. For certain active agents, it is 25 difficult to formulate at relatively high concentrations with sufficient stability. In particular, it is necessary to avoid the appearance of crystals, in particular at low temperature and/or during dilution and/or during storage of the dilute 30 composition at high temperature. The crystals may have harmful effects, especially blocking the filters of the devices used for spreading the dilute composition, blocking the spraying devices, reducing the overall activity of the formulation, creating unnecessary 35 problems of waste-management procedures for removing the crystals, and/or causing.poor distribution of the active product on the agricultural field.

-4 The use of solvent systems based on a single solvent such as N-methylpyrrolidone (NMP) is known. This solvent enables the dissolution of a large number of active agents, and avoids the formation of crystals, but it is, however, considered as presenting hazards, especially for the operatives and users handling it. There is a need for 5 alternative solvent systems that especially have: - great modularity, i.e. the ability to be used for a large number of active agents, - the ability to dissolve large amounts of active agents, - an absence of crystallization, even under rigorous conditions, and/or - a safety, toxicology and/or ecotoxicology profile perceived as being favourable. 10 Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. 15 According to a first aspect, the invention provides a concentrated plant-protection formulation comprising: a) an active plant-protection product, b) a solvent system comprising at least two solvents chosen from the following solvents: 20 bl) an alkyl acetate whose alky group contains at least 3 carbon atoms, b2) a sulfoxide, and b3) a ketone. Optionally, there is at least one emulsifier. Preferably, the emulsifier is a surfactant. Optionally, water is included. 25 This is a concentrated plant-protection formulation. The invention also relates to the use of the formulation (or a method) for preparing a composition diluted in water of the active plant-protection product, by mixing at least one part by weight of concentrated formulation with at least 10 parts and preferably less than 1000 parts of water. Needless to say, the dilute composition may comprise other active plant-protection products, 30 which may be derived from other plant-protection formulations, thus combined in the composition.

-5 The invention also relates to the use of the solvent system in concentrated formulations or in dilute compositions. According to a second aspect, the invention provides use of the formulation as claimed in the first aspect, for preparing a composition diluted in water of the active plant 5 protection product, by mixing at least one part by weight of concentrated formulation with at least 10 parts and preferably less than 1000 parts of water. The invention also relates to a solvent composition that is particularly effective and particularly useful for using the plant-protection formulation, and which can also be used for other purposes. 10 According to a third aspect, the invention provides a solvent composition comprising a mixture of solvents, wherein the composition comprises: - from 20% to 70% of an alkyl acetate solvent bl) whose alkyl group contains at least 3 carbon atoms, - from 20% to 70% by weight of a sulfoxide solvent b2), and 15 - from 10% to 60% by weight of ketone solvent b3). Preferably, the solvent composition comprises 30% to 50% of an alkyl acetate solvent bl) whose alkyl group contains at least 3 carbon atoms, from 25% to 45% by weight of a sulfoxide solvent and 15% to 35% of a ketone solvent. Unless the context clearly requires otherwise, throughout the description and the claims, 20 the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to". Definitions In the present patent application, the term "concentrated plant-protection formulation" 25 means a formulation intended to be mixed with water (for example diluted) by the user, as opposed to a dilute plant-protection composition. In the present patent application, when concentration ranges or percentage proportions in a composition or a formulation are used, the total with optionally other 6 ingredients is 100%. Unless otherwise mentioned, this is a concentration or proportion by weight of active material or of solids. 5 In the present patent application, when concentration ranges or proportions in g/L in a composition or a formulation are used, the total, with optionally other ingredients, is such that it is in accordance with the density of the composition or of the formulation (per 10 1 L, the total is equal to the density x1000). In the present patent application, the term "solid plant-protection product" means a product having a melting point of greater than 25 0 C. 15 Active plant-protection product a) Active plant-protection products, especially solid water-insoluble products, are known to those skilled in 20 the art. The active plant-protection product may especially be an herbicide, an insecticide, an acaricide, a fungicide or a rodenticide, for example a raticide. 25 As nonlimiting examples of suitable active materials, mention may be made, inter alia, of Ametryne, Diuron, Linuron, Chlortoluron, Isoproturon, Nicosulfuron, Metamitron, Diazinon, Aclonifen, Atrazine, Chlorothalonil, Bromoxynil, Bromoxynil heptanoate, 30 Bromoxynil octanoate, Mancozeb, Maneb, Zineb, Phenmedipham, Propanyl, the phenoxyphenoxy series, the heteroaryloxyphenoxy series, CMPP, MCPA, 2,4-D, Simazine, active products of the imidazolinone series, the family of organophosphorus agents, especially with 35 Azinphos-ethyl, Azinphos-methyl, Alachlor, Chlorpyriphos, Diclofop-methyl, Fenoxaprop-p-ethyl, Methoxychlor, Cypermethrin, Fenoxycarb, cymoxanil, 7 chlorothalonyl, neonicotinoid insecticides, the family of triazole fungicides such as azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxyconazole, fenbuconazole, 5 flusilazole, myclobutanyl, tebuconazole, triadimefon, triadimenol, strobilurins such as pyraclostrobin, picoxystrobin, azoxystrobin, famoxadone, kresoxym methyl and trifloxystrobin, sulfonylureas such as bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, 10 metsulfuron-methyl, nicosulfuron, sulfomethuron-methyl, triasulfuron and tribenuron-methyl. From this list, the water-insoluble products are chosen. 15 The active plant-protection product may be chosen in particular from azoles, preferably triazoles, preferably tebuconazole. Tebuconazole is the trivial name of a compound known to those skilled in the art, 20 whose formula is as follows: OH C.H, Tebuconazole is a solid plant-protection product. Triazoles other than tebuconazole that may especially 25 be mentioned include the following compounds: azaconazole; bitertanol; bromuconazole; cyproconazole; diclobutrazol; difenoconazole; diniconazole; diniconazole-M; epoxiconazole; etaconazole; fenbuconazole; fluotrimazole; fluquinconazole; 30 flusilazole; flutriafol; furconazole; furconazole-cis; hexaconazole; imibenconazole; ipconazole; metconazole; 8 myclobutanil; penconazole; prochloraz, propiconazole; prothioconazole; quinconazole; strobulurin and analogues, simeconazole; tetraconazole; triadimefon; triadimenol; triazbutil; triflumizole, triticonazole; 5 uniconazole; uniconazole-P. The active plant-protection product may be chosen in particular from dinitroanilines, for instance pendimethalin or trifluralin. 10 The invention may be particularly advantageously performed for the following active plant-protection products: 9 c!N C12-- Alachlor (' ~ H~-H Chiorpyrifos c 10 H f, H (P*--ai,-&ci r5~) - qc! ei HH alpha cypermethrine i I H. '\H. C as a racemic mixture and/or as isolated stereoisomers Phenmedipham H

HC

10 Propanil ciJ CHO Pendimethalin ~ HrH -. (H C triadimenol . .. .. .... . . ..... Trifluralin F* -,-- .. ~ . NN F Oxyf luorfen I~ _~" . ~ '-NO, DimethoateC-H.

Imidaclopd H Proxopur Genomyl H ILH, Dellamethrin "A. r H 1 H CH 1i 7 . HC Fenvalerate C C

>

12 HH IH H\ (rntor comprrnt II Q .... . ... Abamectin c.,w i Hf.,H- H HICY' H C-H.. Amicarbazone 4 H, J4 -H-CH3 13 F C H CH CH., H H Bifenthrin H H __ CH K F, CH3-CH 2 -- CH -CH 2 Carbosulfan C 3 CCC~.~~ F F H0 ......... ___ Cyfluthn H Ii (7) .5:cs id >,CH~ F F

,.....

14 Difenconazole Ethofenprox Fenoxaprop- .f ethylI : )-CH-c 1- Fipronil c I H C Fenvalerate/ 15 Fluazifop-p-butyl F 3 C 00OHOJH)-~ F, Flufenouron F~* / H S CH~ H r H .

..... Lambda cyalothn l r;('-t4 CH. F. H -T)C Methomyl 16 Permethrin H H~C ~H, . \

CH

2 ' Prochloraz Propiconazole CH2 N \ ....... ....

N--

Tebuconazole -N ( NI e // These products and names are known to those skilled in the art. It would not constitute a departure from the context of the invention to combine several active 5 plant-protection products. Solvent b) and mixture of solvents and solvent composition 10 The solvent system b) comprises several solvents. The 17 solvent system may be introduced in the form of a pre prepared solvent composition. It may also be a combination of solvents introduced individually, or in the form of partial premixes, in the formulation. 5 The term "solvent system" in the plant-protection formulation (or in the dilute composition) means either a mixture prepared prior to the introduction into the formulation, or as a combination, in which the solvents 10 are mixed together while making the formulation, during the placing in contact with the plant-protection active product. The invention also relates to a particularly useful 15 solvent composition comprising a solvent system. In the solvent composition, the solvent mixture is understood as being an effective mixture (as opposed to a combination), which is preferably clear. 20 The solvent system comprises at least two solvents chosen from the following solvents: bl) an alkyl acetate whose alkyl group contains at least 3 carbon atoms, b2) a sulfoxide, 25 b3) a ketone. Preferably, the solvent system comprises the three solvents bl), b2) and b3). 30 The alkyl of solvent bl) is advantageously a C 6

-C

1 5 , preferably C 6

-C

1 3 and preferably C 6

-C

1 2 alkyl. It may especially be a linear, branched or cyclic C6, C7, C8, C9, C10, C1l or C12 or 13 alkyl. It may be a mixture of such alkyls. Mention may preferably be made especially 35 of cyclohexyl or hexyl (n-hexyl), ethylhexyl, especially 2-ethylhexyl, octyl (n-octyl), isooctyl, decyl (n-decyl), isodecyl, tridecyl, dodecyl and 18 undecyl. The sulfoxide b2) is advantageously dimethyl sulfoxide (DMSO). Methyl sulfoxide is an alternative that may be 5 envisioned. The ketone b3) is advantageously acetophenone. According to one preferential mode, the solvent system 10 (or the solvent composition) used comprises the following solvents: bl) cyclohexyl acetate b2) dimethyl sulfoxide (DMSO) b3) acetophenone. 15 This solvent system may be used by introducing the various solvents separately. It may be used in the form of a solvent composition. 20 In a particularly advantageous manner, the solvent system (or the solvent composition) comprises: - from 20% to 70% and preferably from 30% to 50% by weight of solvent bl), - from 20% to 70% and preferably from 25% to 45% by 25 weight of solvent b2), - from 10% to 60% and preferably from 15% to 35% by weight of solvent b3), these amounts being expressed relative to the sum of the solvents bl), b2) and b3), equal to 100%. 30 For example, the solvent system (or the solvent composition) is a "preferred solvent system" comprising: - from 30% to 50% by weight of cyclohexyl or ethylhexyl 35 acetate, - from 25% to 45% by weight of dimethyl sulfoxide, - from 15% to 35% by weight of acetophenone.

19 Preferably, the weight amount of the solvent b3), in particular of acetophenone, relative to the sum of the solvents bl), b2) and b3), equal to 100%, is less than 5 25%, for example between 10% and 25% and preferably between 15% and 25%. It is pointed out that, in general, the solvent composition comprises substantially no water (typically 10 less than 5% by weight and preferably less than 1% by weight), and that it comprises substantially no active plant-protection product (typically less than 5% by weight and preferably less than 1% by weight). It is not excluded for it to comprise other solvents 15 (different than water) and/or at least one surfactant. Emulsifier c) The plant-protection formulation may comprise an 20 emulsifier, typically and preferably a surfactant. Emulsifiers are agents intended for facilitating emulsification or dispersion after placing the formulation in contact with water, and/or for stabilizing (over time and/or with respect to 25 temperature) the emulsion or dispersion, for example by avoiding sedimentation. Surfactants are known compounds, which generally have a relatively low molar mass, for example of less than 30 1000 g/mol. The surfactant may be an anionic surfactant in salified or acidic form, a nonionic surfactant, which is preferably polyalkoxylated, or a cationic or amphoteric surfactant (this term also including zwitterionic surfactants). It may be a mixture or a 35 combination of these surfactants. As examples of anionic surfactants, mention may be 20 made, without wishing to be limited thereto, of: - alkylsulfonic acids and arylsulfonic acids, optionally substituted with one or more hydrocarbon based groups, and whose acid function is partially or 5 totally salified, for instance C 8

-C

50 , more particularly

C

8 -C30 and preferably C10-C 2 2 alkylsulfonic acids, benzenesulfonic acids, naphthalenesulfonic acids, substituted with one to three C 1

-C

3 0 and preferably C 4 C 16 alkyl and/or C 2 -C30 and preferably C 4

-C

1 6 alkenyl 10 groups, - alkylsulfosuccinic acid mono- or diesters, in which the linear or branched alkyl part is optionally substituted with one or more hydroxyl and/or linear or branched C 2

-C

4 alkoxy (preferably ethoxy, propoxy or 15 ethopropoxy) groups, - phosphate esters more particularly chosen from those comprising at least one saturated, unsaturated or aromatic, linear or branched hydrocarbon-based group containing 8 to 40 and preferably 10 to 30 carbon 20 atoms, optionally substituted with at least one alkoxy (ethoxy, propoxy or ethopropoxy) group. In addition, they comprise at least one mono- or diesterified phosphate ester group, such that one or two free or partially or totally salified acid groups may be 25 present. The preferred phosphate esters are mono- and diesters of phosphoric acid and of alkoxylated (ethoxylated and/or propoxylated) mono-, di- or tristyrylphenol, or of alkoxylated (ethoxylated and/or propoxylated mono-, di- or trialkylphenol, optionally 30 substituted with one to four alkyl groups; of phosphoric acid and of a CB-C3o and preferably C 10

-C

22 alkoxylated (ethoxylated or ethopropoxylated) alcohol; of phosphoric acid and of a C 8

-C

2 2 and preferably C 10

-C

2 2 non-alkoxylated alcohol, 35 - sulfate esters obtained from saturated or aromatic alcohols, optionally substituted with alkoxy (ethoxy, propoxy or ethopropoxy) groups, and for which the 21 sulfate functions are in free acid or partially or totally neutralized form. Examples that may be mentioned include the sulfate esters more particularly obtained from saturated or unsaturated CB-C 2 0 alcohols, 5 which may comprise 1 to 8 alkoxy (ethoxy, propoxy or ethopropoxy) units; the sulfate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 saturated or unsaturated C 2

-C

3 0 hydrocarbon-based groups, and in which the number of alkoxy units is 10 between 2 and 40; and the sulfate esters obtained from polyalkoxylated mono-, di- or tristyrylphenol, in which the number of alkoxy units ranges from 2 to 40. The anionic surfactants may be in acid form (they are 15 potentially anionic), or in a partially or totally salified form, with a counterion. The counterion may be an alkali metal, such as sodium or potassium, an alkaline-earth metal, such as calcium, or an ammonium ion of formula N(R) 4 + in which R, which may be identical 20 or different, represent a hydrogen atom or a C 1

-C

4 alkyl radical optionally substituted with an oxygen atom. Examples of nonionic surfactants that may be mentioned, without wishing to be limited thereto, include: 25 - polyalkoxylated (ethoxylated, propoxylated or ethopropoxylated) phenols substituted with at least one

C

4

-C

20 and preferably C 4 -C1 2 alkyl radical, or substituted with at least one alkylaryl radical in which the alkyl part is Ci-C 6 . More particularly, the 30 total number of alkoxy units is between 2 and 100. Examples that may be mentioned include polyalkoxylated mono-, di- or tri(phenylethyl)phenols, or polyalkoxylated nonylphenols. Among the ethoxylated and/or propoxylated, sulfated and/or phosphated di- or 35 tristyrylphenols, mention may be made of ethoxylated di(1-phenylethyl)phenol, containing 10 oxyethylene units, ethoxylated di (1-phenylethyl)phenol, containing 22 7 oxyethylene units, sulfated ethoxylated tri(1 phenylethyl)phenol, containing 7 oxyethylene units, ethoxylated tri(1-phenylethyl)phenol, containing 8 oxyethylene units, ethoxylated tri(1 5 phenylethyl)phenol, containing 16 oxyethylene units, sulfated ethoxylated tri(1-phenylethyl)phenol, containing 16 oxyethylene units, ethoxylated tri(1 phenylethyl)phenol, containing 20 oxyethylene units and phosphated ethoxylated tri(1-phenylethyl)phenol, 10 containing 16. oxyethylene units, - polyalkoxylated (ethoxylated, propoxylated or ethopropoxylated) C 6

-C

22 fatty alcohols or fatty acids. The number of alkoxy units is between 1 and 60. The term "ethoxylated fatty acid" includes not only the 15 product obtained by ethoxylation of a fatty acid with ethylene oxide, but also those obtained by esterification of a fatty acid with a polyethylene glycol, - polyalkoxylated (ethoxylated, propoxylated or 20 ethopropoxylated) triglycerides of plant or animal origin. Thus, triglycerides derived from lard, tallow, groundnut oil, butter oil, cottonseed oil, linseed oil, olive oil, almond oil, grapeseed oil, fish oil, soybean oil, castor oil, rapeseed oil, copra oil or coconut 25 oil, and comprising a total number of alkoxy units of between 1 and 60, are suitable for use. The term "ethoxylated triglyceride" covers not only the product obtained by ethoxylation of a triglyceride with ethylene oxide, but also those obtained by 30 transesterification of a triglyceride with a polyethylene glycol, - optionally polyalkoxylated (ethoxylated, propoxylated or ethopropoxylated) sorbitan esters, more particularly cyclized sorbitol esters of C10-C 2 0 fatty acids such as 35 lauric acid, stearic acid or oleic acid, and comprising a total number of alkoxy units of between 2 and 50.

23 The emulsifiers that are useful are especially the following products, all sold by Rhodia: - Soprophor@ TSP/724: surfactant based on ethopropoxylated tristyrylphenol 5 - Soprophor® 796/0: surfactant based on ethopropoxylated tristyrylphenol - Soprophor® CY 8: surfactant based on ethoxylated tristyrylphenol - Soprophor® BSU: surfactant based on ethoxylated 10 tristyrylphenol - Alkamuls® RC: surfactant based on ethoxylated castor oil - Alkamuls® OR/36: surfactant based on ethoxylated castor oil 15 - Alkamuls® T/20: surfactant based on a sorbitan ester - Geronol® RH-796: mixture of surfactants - Soprophor@ TS/10: surfactant based on ethoxylated tristyrylphenol - Geronol® FF/4-E: mixture of surfactants 20 - Geronol® TE/777: mixture of surfactants Rhodacal® 60/BE: calcium dodecylbenzenesulfonate - Geronol® TBE/724: mixture of surfactants - Geronol® PVA: mixture of surfactants - Antarox® B/848: ethylene oxide/propylene oxide block 25 copolymer - Geronol® FF/6-E: mixture of surfactants The formulation advantageously comprises at least 4%, preferably at least 5% and preferably at least 8%, by 30 weight of solids, of at least one surfactant c). Without wishing to be bound to any theory, it is thought that the solvent system is advantageously associated with relatively large amounts of solvent compared with what may usually be used for formulations 35 comprising NMP. In addition, it is thought that this may be linked to a relatively high affinity for water.

24 It is mentioned that the solvent system (or the solvent composition) may be combined with an aromatic and/or nonaromatic surfactant. 5 Formulation The concentrated formulation does not comprise large amounts of water. Typically, the water content is less than 50% by weight and advantageously less than 25% by 10 weight. It will generally be less than 10% by weight. The formulation is preferably a liquid formulation, for example in the form of an emulsifiable concentrate (EC), a concentrated emulsion (CE) or a microemulsion 15 (ME) . In this case, it preferably comprises less than 500 g/L and more preferably less than 250 g/L of water. It will generally be less than 100 g/L. The formulations may advantageously comprise: 20 a) from 4% to 60% and preferably from 10% to 50%, of the plant-protection product, by weight of active material, b) from 10% to 92% and preferably from 20% to 80%, of the solvent system, by weight, 25 c) from 4% to 60%, preferably from 5% to 50% and preferably from 8% to 25%, by weight of solids, of an emulsifier, preferably of a surfactant, d) from 0 to 10% by weight of water. 30 According to one particular embodiment, the formulation comprises: - from 15% to 35% by weight of tebuconazole, - from 40% to 65% by weight of the preferred solvent system, 35 - from 5% to 15% by weight of solids of at least one surfactant, and - optionally up to 20% of another additive.

25 According to another particular embodiment, the formulation comprises: - from 15% to 35% by weight of oxyfluorfen, 5 - from 50% to 75% by weight of the preferred solvent system, - from 5% to 15% by weight of solids of at least one surfactant, and - optionally up to 10% of another additive. 10 According to another particular embodiment, the formulation comprises: - from 25% to 45% by weight of propanil, - from 25% to 45% by weight of the preferred solvent 15 system, - from 10% to 25% by weight of solids of at least one surfactant, and' - optionally up to 20% of another additive. 20 According to another particular embodiment, the formulation comprises: - from 10% to 25% by weight of phenmedipham, - from 35% to 55% by weight of the preferred solvent system, 25 - from 10% to 25% by weight of solids of at least one surfactant, and - optionally up to 30% of another additive, preferably from 10% to 30% of another solvent and/or of a crystallization inhibitor. 30 It is not excluded to prepare solid formulations, for example formulations in which a liquid comprising the plant-protection product dissolved in the solvent or the mixture of solvents or the solvent composition is 35 supported by a mineral and/or dispersed in a solid matrix.

26 Needless to say, the formulation may comprise other ingredients (or "other additives") other than the active plant-protection product, the solvent(s), the optional emulsifier(s) and the optional water. It may 5 especially comprise viscosity modifiers, antifoams, especially silicone antifoams, debouncing agents, anti leaching agents, inert fillers, especially mineral fillers, antifreezes, etc. 10 The formulations may especially comprise additives, referred to as other additives, not included in the definition of the products a), b) or c), for instance: - other solvents, generally in small amount, for example in an amount less than the amount of solvents 15 bl), b2) and b3), i.e. in an amount less than that of the solvent of the solvent system that is present in the smallest amount. An "other solvent" is not understood as forming part of the solvent system. Examples of other solvents that may especially be 20 mentioned include solvents of the phosphate, phosphonate or phosphine oxide family, for instance TEBP, TBP, TEPO and DBBP. Mention is also made of alkyldimethylamides in which the alkyl is C 6 -Ci 8 , especially those sold under the brand name Genagen®. 25 Mention is also made of ester lactates, especially those sold under the brand name Purasolv®. Mention is also made of fatty acid methyl esters, especially those sold under the brand name Phytorobe®. Mention is also made of diesters of diacids (dibasic esters), 30 especially those sold by Rhodia under the brand names Rhodiasolv® RPDE and Rhodiasolv® DIB. Hydrocarbon fractions, cyclic amides and lactones are also mentioned; - crystallization inhibitors. These may be the solvents 35 mentioned above. They may also be non-polyalkoxylated fatty acids or fatty alcohols. An example that is mentioned is the product Alkamuls® OL700.

27 Process Standard processes for preparing plant-protection 5 formulations or solvent mixtures may be used. The process may be performed by simple mixing of the constituents. It is especially possible to introduce the various 10 solvents separately. A solvent mixture prepared beforehand, typically the solvent composition, may also be introduced. The solvent composition may be prepared by simple 15 mixing of the solvents. Use of the plant-protection formulation The concentrated plant-protection formulation is 20 intended to be spread on a cultivated field or a field to be cultivated, for example a field of soybean, usually after diluting in water, to obtain a dilute composition. The dilution is generally performed by the farmer, directly in a tank (tank mix), for example in 25 the tank of a device for spreading the composition. It is not excluded for the farmer to add other plant protection products, for example fungicides, herbicides, pesticides, insecticides or fertilizers. Thus, the formulation may be used to prepare a 30 composition diluted in water of the active plant protection product, by mixing at least one part by weight of concentrated formulation with at least 10 parts and preferably less than 1000 parts of water. The dilution rates and the amounts to be applied on the 35 field generally depend on the plant-protection product and on the desirable dose for treating the field; this may be determined by the farmer.

28 Other details or advantages of the invention will emerge in the light of the examples that follow, which are given without any limiting nature. 5 EXAMPLES The following ingredients are used: - cyclohexyl acetate 10 - 2-ethylhexyl acetate - DMSO - acetophenone - Oxyfluorfen: at 95-98% active material - Tebuconazole: at 96.34% active material 15 - Phenmedipham: at 95-97% active material - Triadimenol: at 95-97% active material - Propoxur: at 97-99% active material - Propanil: at 97-99% active material - Pendimethalin: at 95% active material 20 - Trifluralin - Imidacloprid - Dimethoate - Geronol® TBE724, Rhodia: surfactant comprising more than 50% by weight of ethopropoxylated tristyrylphenol 25 - Geronol® TE/300, Rhodia: proprietary surfactant mixture comprising ethoxylated castor oil and an ethopropoxylated alcohol - Alkamuls@ RC, Rhodia: ethoxylated castor oil surfactant 30 - Geronol® PR/500, Rhodia: proprietary surfactant mixture - Geronol® VB/999, Rhodia: proprietary surfactant mixture - Rhodiasolv® ADMA10, Rhodia (Asia-Pacific region): 35 alkyldimethylamide solvent - Alkamuls® OL/700, Rhodia: oleic acid 29 Examples 1 to 6 The following solvent systems are prepared: Example 1 2 3 4 5 6 7 Solvent MIX 1 MIX 2 MIX 3 MIX 4 MIX 5 MIX 6 MIX 7 Acetophenone (AP) 27.4 24.5 50 50 0 24.5 24.5 Cyclohexyl acetate (CA) 37.0 40.0 50 0 50 0 0 DMSO 35.6 35.5 0 50 50 35.5 35.5 2-Ethylhexyl acetate 0 0 0 0 0 40.0 40.0 Decyl acetate 0 0 0 0 0 0 0 5 Examples 8 to 16 - Tebuconazole By mixing together the ingredients, formulations containing 25% tebuconazole of emulsifiable concentrate 10 (EC) type are prepared. The formulations comprise 25% by weight (of active material) of tebuconazole and 10% by weight of Alkamuls® RC surfactant, the remainder being solvent. 15 The following tests are performed: - Visual observation at 25 0 C - The appearance of the formulation is noted and the possible presence of crystals is investigated - Visual observation at 00C - The formulation is placed 20 for seven days at 0 0 C, and the appearance of the formulation is noted and the possible presence of crystals is investigated (test CIPAC MT39) - Visual observation at 00C with nucleation: a crystal of the active material is introduced into the 25 formulation that has spent 7 days at 0 0 C for nucleation, and the formulation is placed at 00C for a further 7 days. The appearance of the formulation is noted and the possible presence of crystals is investigated.

30 Example Solvent Appearance Appearance Appearance at 0*C system at 25 0 C at 0*C with nucleation 8C 100% Cloudy Crystals / acetophenone 9C 100% DMSO Clear Crystals / 10 MIX 3 Clear Clear Crystals 11 MIX 4 Clear Clear Crystals 12 MIX 5 Clear Clear Crystals 13 Mix 1 Clear Clear Clear 14 Mix 2 Clear Clear Clear 15 MIX 6 Clear Clear Clear 16 MIX 7 Clear Clear Clear The letter C indicates that it is a comparative example These examples show that: 5 - the two-solvent combinations allow the formulations to be improved (no crystals at 0*C) - the three-solvent combinations allow the formulations to be further improved (no crystals at 0*C with nucleation) 10 Examples 17 to 21 - Oxyfluorfen By mixing together the ingredients, formulations containing 22% oxyfluorfen of emulsifiable concentrate 15 (EC) type are prepared. The formulations comprise 22% by weight (of active material) of oxyfluorfen and 10% by weight of AlkamulsO RC surfactant, the remainder being solvent. Example Solvent Appearance Appearance Appearance at 0*C system at 25 0 C at O'C with nucleation 17C 100% Clear Clear Crystals acetophenone 18C 100% DMSO Clear Solid / 31 19 MIX 4 Clear Clear Crystals 20 Mix 1 Clear Clear Clear 21 Mix 2 Clear Clear Clear The letter C indicates that it is a comparative example These examples show that: - the two-solvent combinations allow the formulations 5 to be improved (no crystals at 0*C) - the three-solvent combinations allow the formulations to be further improved (no crystals at 0"C with nucleation) 10 Examples 22 to 32 - Other active agents By mixing together the ingredients, formulations of various plant-protection active agents of emulsifiable concentrate (EC) type are prepared. The formulations 15 comprise: - the active agent, in the amount by weight (of active material) indicated in the table below, - 10% by weight of Alkamuls@ RC surfactant, - the remainder being the solvent "Mix 2". 20 Example Active agent Appearance Appearance Appearance at 25 0 C at 0 0 C at 0*C with nucleation 22 Phenmedipham - 16% Clear Clear Clear 23 Triadimenol - 23% Clear Clear Clear 24 Propoxur - 20% Clear Clear Clear 25 Alachlor - 48% Clear Clear / 26 Chlorpyriphos - 40% Clear Clear Clear 27 Alpha-cypermethrin - 10% Clear Clear Clear 28 Pendimethalin - 33% Clear Clear / 29 Trifluralin - 40% Clear Clear Clear 30 Dimethoate - 40% Clear Clear Clear 31 Propanil - 36% Clear Clear Clear 32 32 Imidacloprid - 20% Clear -Clear / Examples 33 to 42 - Other active agents By mixing together the ingredients, formulations of 5 various plant-protection active agents of emulsifiable concentrate (EC) type are prepared. The formulations comprise: - the active agent, in the amount by weight (of active material) indicated in the table below, 10 - 10% by weight of Alkamuls® RC surfactant, - the remainder being the solvent "Mix 6". Example Active agent Appearance Appearance Appearance at 25 0 C at 0 0 C at 0*C with nucleation 33 Phenmedipham - 16% Clear Clear Clear 34 Triadimenol - 23% Clear Clear / 35 Propoxur - 20% Clear Clear Clear 36 Alachlor - 48% Clear Clear / 37 Chlorpyriphos - 40% Clear Clear Clear 38 Alpha-cypermethrin - 10% Clear Clear Clear 39 Pendimethalin - 33% Clear Clear / 40 Trifluralin - 40% Clear Clear Clear 41 Dimethoate - 40% Clear Clear Clear 42 Propanil - 36% Clear Clear Clear Examples 43 to 48 - Other active agents 15 By mixing together the ingredients, formulations of various plant-protection active agents of emulsifiable concentrate (EC) type are prepared. The formulations comprise: 20 - the active agent, in the amount by weight (of active material) indicated in the table below, - 10% by weight of Alkamuls@ RC surfactant, 33 - the remainder being the solvent "Mix 7". Example Active agent Appearance Appearance Appearance at 0*C at 25 0 C at 0*C with nucleation 43 Phenmedipham - 16% Clear Clear Clear 44 Propoxur - 20% Clear Clear Clear 45 Chlorpyriphos - 40% Clear Clear Clear 46 Trifluralin - 40% Clear Clear Clear 47 Dimethoate - 40% Clear Clear Clear 48 Propanil - 36% Clear Clear Clear Example 49 - Optimized formulations 5 By mixing together the ingredients, formulations of various plant-protection active agents of emulsifiable concentrate (EC) type are prepared. The ingredients and their amounts are indicated below. All the ingredients 10 marked with a 0 are available from Rhodia. 49.1 EC Oxyfluorfen 23% - Oxyfluorfen 24.2% (as supplied) - Mix 2 65.8% 15 - Geronol® TBE 724 10% (as supplied) 49.2 EC Tebuconazole 25% (250 g/L) - Tebuconazole 26.2% (261 g/L) (as supplied) - Mix 2 53.8% (535 g/L) 20 - Geronol® TE/300 10% (100 g/L) (as supplied) - Alkamuls® OL/700 10% (100 g/L) (as supplied) 49.3 EC Propanil 36% - Propanil 36.7% (as supplied) 25 - Mix 2 35.3% - Geronol® PR/500 18% (as supplied) - Alkamuls® OL/700 10% (100 g/L) (as supplied) 49.4 EC Phenmedipham 16% 34 - Phenmedipham 16.5% (as supplied) - Mix 2 43.5% - Rhodiasolv® ADMA10 20% (as supplied) - Geronol® VB/999 20% (as supplied) 5 49.5 EC Fenvalerate 20% - Fenvalerate tech. 94% 21.3% - Mix 2 70.7% - Geronol@ TBE/724 8% 10 49.6 EC Deltamethrin 5%C - Deltamethrin tech. 98% 5.1% - Mix 2 84.9% - Rhodacal® 60/BE 3% 15 - Soprophor® 796/P 7% 49.7 EC Benomyl 19% - Benomyl tech. 98% 19.4% - Mix 2 75.6% 20 - Soprophor® TSP/724 4.5% - Rhodacal® 60/BE 0.5% 49.8 EC Trifluralin 480 g/L - Trifluralin tech. 96% 500 g/L 25 - Mix 2 550 g/L - Geronol® TFG/48 100 g/L 49.9 EC Abamectin 18 g/L - Abamectin tech. 97% 19 g/L 30 - MIX 6 875 g/L - Geronol® RH-796 100 g/L -49.10 EC Amicarbazone 25% - Amicarbazone tech. 96% 25.5% 35 - MIX 6 59.5% - Soprophor@ TS/10 12% - Geronol@ FF/4-E 3% 35 49.11 EC Alpha-Cypermethrin 10% - Alpha-Cypermethrin tech. 93% 11% - MIX 6 79% 5 - Geronol® TE/300 10% 49.12 EC Bifenthrin 100 g/L - Bifenthrin tech. 98% 102 g/L - MIX 6 806 g/L 10 - Geronol® TE/300 100 g/L 49.13 EC Carbosulfan 250 g/L - Carbosulfan tech. 90% 278 g/L - MIX 6 584 g/L 15 - Geronol® TE/300 150 g/L 49.14 EC Cyfluthrin 100 g/L - Cyfluthrin tech. 98.5% 102 g/L - MIX 6 815 g/L 20 - Geronol® TE/300 100 g/L 49.15 EC Cypermethrin 200 g/L - Cypermethrin tech. 98% 218 g/L - MIX 6 714 g/L 25 - Geronol® TBE/724 100 g/L 49.16 EC Difenconazole 250 g/L - Difenconazole tech. 95.5% 262 g/L - MIX 6 698 g/L 30 - Geronol® FF/4-E 5 g/L - Geronol@ FF/6-E 95 g/L 49.17 EC Deltamethtrin 5% - Deltamethtrin tech. 98% 5.1% 35 - MIX 2 54.9% - Methyl ester 30% - Rhodacal@ 60/BE 3.5% 36 - Geronol TE/777 6.5% 49.18 EC Etofenprox 30% - Etofenprox tech. 98% 30.6% 5 - MIX 2 59.4% - Geronol® TE/300 10% 49.19 EC Fenoxaprop-ethyl 10% - Fenvalerate tech. 95% 10.6% 10 - MIX 6 66.4% - RhodiasolvO RPDE 15% - Geronol® TE/300 8% 49.20 EC Fipronil 5% 15 - Fipronil tech. 96% 5.2% - MIX 6 59.8% - Rhodiasolv@ RPDE 25% - Geronol® ND-80 10% 20 49.21 EC Fluazifop-p-butyl 125 g/L - Fluazifop-p-butyl tech. 93% 135 g/L - MIX 6 778 g/L - Geronol® TE/300 100 g/L 25 49.22 EC Flufenoxuron 50 g/L - Flufenoxuron tech. 98% 51 g/L - MIX 6 628 g/L - Geronol® TE/300 100 g/L 30 49.23 EC Flufenoxuron 100 g/L - Flufenoxuron tech. 98% 102 g/L - MIX 6 822 g/L - Geronol® TE/300 100 g/L 35 49.24 EC Hexaxinone 250 g/L - Hexaxinone tech. 97% 258 g/L - MIX 2 682 g/L 37 - Geronol® TE/777 100 g/L 49.25 EC Lambda-cyalothrin 110 g/L - Lambda-cyalothrin tech. 95% 116 g/L 5 - MIX 6 794 g/L - Geronol® TE/300 100 g/L 49.26 EC Metomyl 190 g/L - Metomyl tech. 98% 195 g/L 10 - MIX 2 650 g/L - Rhodiasolv@ RPDE 180 g/L - Rhodacal@ 60/BE 2.5 g/L - Soprophor® TSP/724 47.5 g/L 15 49.27 EC Oxyfluorfen 22% - Oxyfluorfen tech. 95% 23.2% - MIX 2 69.3% - Geronol® TBE/724 6.5% - Geronol® PVA 1% 20 49.28 EC Permethrin 200 g/L - Permethrin tech. 95% 211 g/L - MIX 6 725 g/L - Geronol@ TE/300 100 g/L 25 49.29 EC Prochloraz 370 g/L - Prochloraz tech. 97.5% 380 g/L - MIX 6 613 g/L - Soprophor® CY8 60 g/L 30 - Antarox@ B/848 10 g/L - Rhodacal® 60/BE 30 g/L 49.30 EC Propiconazole 250 g/L - Propiconazole tech. 95% 264 g/L 35 - MIX 6 686 g/L - Geronol® FF/4-E 15 g/L - Geronol® FF/6-E 85 g/L 38 49.31 EC Propoxur 20% - Propoxur tech. 98% 20.4% - MIX 2 69.6% 5 - Geronol® FF/4-E 3.5% - Alkamuls® OR/36 6.5% 49.32 EC Tebuconazole 200 g/L - Tebuconazole tech. 93% 215 g/L 10 - MIX 6 575 g/L - Geronol® TE/300 200 g/L - Alkamuls@ OL/700 50 g/L 49.33 EC Triadimenol 23% 15 - Triadimenol tech. 95% 24.2% - MIX 2 49.8% - Rhodiasolv® ADMA 10 17% - Antarox® B/848 10% 20 Example 50 - Optimized formulation and emulsification data By mixing together the ingredients, the emulsifiable concentrate (EC) below is prepared. 25 EC Tebuconazole 25% (250 g/L) - Tebuconazole tech. 96% 25% (active agent) (260.1 g/L) (as supplied) - MIX 6 51% (529.5 g/L) 30 - Geronol@ TE/300 14.4% (150 g/L) (as supplied) - Alkamuls® OL/700 9.6% (100 g/L) (as supplied) The following tests were performed: - pH: test CIPAC MT75 35 - Density at 20'C - Stability after dilution ("Emulsification"): test CIPAC MT36, performed at concentrations after dilution 39 of 0.1%, 1% and 5% at 30'C, before (at 2 hours and 24 hours of emulsification) and after storage for 14 days at 54 0 C, with water hardnesses A (20 ppm), D (342 ppm), C (500 ppm) or 1000 ppm 5 - Test of appearance of the formulation at 0*C or at 54 0 C: test CIPAC MT39 (0*C) and MT46 (54 C). The results are as follows: - Density at 20*C: 1.040 10 - pH (5% sol.): 6.4 - Emulsification (dilution): A D C Emulsification OK OK OK 0.1%, 30 0 C, after 2 hours Emulsification OK OK OK 0.1%, 30'C, after 24 hours Emulsification OK OK OK 1%, 30'C, after 2 hours Emulsification OK OK OK 1%, 30 0 C, after 24 hours Emulsification OK OK OK 5%, 30"C, after 2 hours Emulsification OK OK OK 5%, 30 0 C, after 24 hours After 14 days at 54'C OK OK OK Emulsification 0.1%, 30 0 C, after 2 hours After 14 days at 54 0 C OK OK OK Emulsification 5%, 30"C, after 2 hours - Appearance at 0*C: clear solution, OK - Appearance at 54 0 C: clear solution, OK

Claims

1. A concentrated plant-protection formulation comprising: a) an active plant-protection product, b) a solvent system comprising at least two solvents chosen from the following 5 solvents: bl) an alkyl acetate whose alkyl group contains at least 3 carbon atoms, b2) a sulfoxide, and b3) a ketone.

2. The formulation according to claim 1 further comprising at least one emulsifier 10 3. The formulation according to claim 2, wherein the emulsifier is a surfactant.

4. The formulation according to any one of claims I to 3 further comprising water.

5. The formulation as claimed in any one of claims I to 4, wherein the solvent system comprises the three solvents bl), b2) and b3).

6. The formulation as claimed in any one of the preceding claims, wherein the alkyl 15 of the solvent bl) is a C 6 -C 12 alkyl.

7. The formulation according to claim 6 wherein the alkyl of the solvent bl) is cyclohexyl, hexyl, ethylhexyl, octyl, isooctyl, decyl or isodecyl.

8. The formulation as claimed in any one of the preceding claims, wherein the sulfoxide b2) is dimethyl sulfoxide (DMSO). 20 9. The formulation as claimed in any one of the preceding claims, wherein the ketone b3) is acetophenone.

10. The formulation as claimed in any one of the preceding claims, wherein the solvent system comprises the following solvents: bl) cyclohexyl acetate, 25 b2) dimethyl sulfoxide (DMSO), and b3) acetophenone, - 41 I1. The formulation as claimed in any one of the preceding claims, wherein the solvent system comprises: - from 20% to 70% by weight of solvent bl), - from 20% to 70% by weight of solvent b2), and 5 - from 10% to 60% by weight of solvent b3), these amounts being expressed relative to the sum of the solvents bl), b2) and b3), equal to 100%.

12. The formulation as claimed in claim 11, wherein the solvent system comprises: - from 30% to 50% by weight of solvent bl), 10 - from 25% to 45% by weight of solvent b2), and - from 15% to 35% by weight of solvent b3).

13. The formulation as claimed in claim 12, wherein the solvent system comprises: - from 30% to 50% by weight of cyclohexyl acetate, - from 25% to 45% by weight of dimethyl sulfoxide, and 15 - from 15% to 35% by weight of acetophenone.

14. The formulation as claimed in any one of the preceding claims, wherein the active plant-protection product is an herbicide, an insecticide, an acaricide, a rodenticide or a fungicide.

15. The formulation as claimed in any one of the preceding claims, wherein the active 20 plant-protection product is chosen from the following compounds: - Alachlor, - Chlorpyriphos, - alpha-Cypermethrin, - Phenmedipham, 25 - Propanil, - Pendimethalin, - azoles, - Triadimenol, - Trifluralin, 30 - Oxyfluorfen, - Imidacloprid, - 42 - Dimethoate, and - Propoxur.

16. The formulation as claimed in claim 15, wherein said azole is a triazole.

17. The formulation as claimed in claim 16, wherein said triazole is tebuconazole. 5 18. The formulation as claimed in any one of the preceding claims, wherein the formulation comprises at least 4% by weight of solids, of at least one surfactant c).

19. The formulation as claimed in claim 18, wherein the formulation comprises at least 5% by weight of solids, of at least one surfactant c).

20. The formulation as claimed in claim 19, wherein the formulation comprises at least 10 8% by weight of solids, of at least one surfactant c).

21. The formulation as claimed in any one of the preceding claims, wherein the formulation comprises: a) from 4% to 60% of the plant-protection product, by weight of active material, b) from 10% to 92% by weight of solvent system, 15 c) from 4% to 60% by weight of solids, of an emulsifier, and d) from 0 to 10% by weight of water.

22. The formulation as claimed in claim 21, wherein the formulation comprises: a) from 10% to 50% of the plant-protection product, by weight of active material, b) from 20% to 80% by weight of solvent system, 20 c) from 5% to 50% by weight of solids, of an emulsifier, and d) from 0 to 10% by weight of water.

23. The formulation as claimed in claim 22, wherein the formulation comprises 8% to 25% by weight of solids of an emulsifier

24. The formulation as claimed in claim 23, wherein the emulsifier is a surfactant. 25 25. The formulation as claimed in any one of the preceding claims, wherein the formulation comprises: - from 15% to 35% by weight of tebuconazole, - 43 - from 40% to 65% by weight of the solvent system as claimed in claim 13, - from 5% to 15% by weight of solids of at least one surfactant.

26. The formulation as claimed in claim 25, wherein the formulation further comprises up to 20% of another additive. 5 27. The formulation as claimed in any one of claims I to 21, wherein the formulation comprises: - from 15% to 35% by weight of oxyfluorfen, - from 50% to 75% by weight of the solvent system as claimed in claim 13, - from 5% to 15% by weight of solids of at least one surfactant. 10 28. The formulation as claimed in claim 27, wherein the formulation further comprises up to 10% of another additive.

29. The formulation as claimed in any one of claims I to 21, wherein the formulation comprises: - from 25% to 45% by weight of Propanil, 15 - from 25% to 45% by weight of the solvent system as claimed in claim 13, - from 10% to 25% by weight of solids of at least one surfactant.

30. The formulation as claimed in claim 29, wherein the formulation further comprises up to 20% of another additive.

31. The formulation as claimed in any one of claims I to 21, wherein the formulation 20 comprises: - from 10% to 25% by weight of Phenmedipham, - from 35% to 55% by weight of the solvent system as claimed in claim 13, - from 10% to 25% by weight of solids of at least one surfactant.

32. The formulation as claimed in claim 31, wherein the formulation further comprises 25 up to 30% of another additive.

33. The formulation as claimed in claim 32, wherein said additive is from 10% to 30% of another solvent and/or of a crystallization inhibitor. - 44 34. The formulation as claimed in any one of the preceding claims, wherein the formulation comprises a surfactant c), the surfactant being chosen from non-ionic surfactants, anionic surfactants and amphoteric surfactants, and mixtures or combinations thereof. 5 35. The formulation as claimed in any one of the preceding claims, wherein the formulation is in the form of an emulsifiable concentrate, a concentrated emulsion or a microemulsion, comprising less than 500 g/L of water.

36. Use of the formulation as claimed in any one of the preceding claims, for preparing a composition diluted in water of the active plant-protection product, by 10 mixing at least one part by weight of concentrated formulation with at least 10 parts and preferably less than 1000 parts of water.

37. A solvent composition comprising a mixture of solvents, wherein the composition comprises: - from 20% to 70% of an alkyl acetate solvent bl) whose alkyl group contains at 15 least 3 carbon atoms, - from 20% to 70% by weight of a sulfoxide solvent b2), and - from 10% to 60% by weight of ketone solvent b3).

38. A solvent composition comprising a mixture of solvents as claimed in claim 37, wherein the composition comprises: 20 - from 30% to 50% by weight of an alkyl acetate solvent bl) whose alkyl group contains at least 3 carbon atoms, - from 25% to 45% by weight of a sulfoxide solvent b2), and - from 15% to 35% by weight of ketone solvent b3).

39. The solvent composition as claimed in claim 37 or claim 38, wherein the 25 composition comprises: bl) from 30% to 50% by weight of cyclohexyl or ethylhexyl acetate, b2) from 25% to 45% by weight of dimethyl sulfoxide (DMSO), and b3) from 15% to 35% by weight of acetophenone.

40. The solvent composition according to any one of claims 37 to 39, wherein the 30 composition comprises: - 45 - substantially no water, - substantially no active plant-protection product. 40. The solvent composition as claimed in claim 36, wherein the composition comprises other solvents and/or surfactant. 5 41. A concentrated plant-protection formulation substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying examples.

42. Use of the formulation substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying examples. 10 43. A solvent composition substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying examples.