WO2019068914A1 - Formulations comprising surfactants, organic liquids and viscosifiers - Google Patents

Abstract

The invention relates to a non-aqueous emulsifiable formulation comprising a) at least 3% by weight of at least one surfactant, b) at least 10% by weight of an organic liquid, c) at least 0.1% by weight of at least one viscosity enhancer selected from N-hydrocarbyldiamides or mixtures thereof.

Description

Formulations comprising surfactants, organic liquids and viscosifiers

[0001] This application claims priority to European patent application

No. 17306341.3 filed on October 5, 2017, the whole content of this application being incorporated herein by reference for all purposes.

[0002] The present invention relates to formulations comprising surfactants,

organic liquids and viscosifiers.

[0003] Such formulations are useful for the manufacture of compositions

comprising biologically active ingredients, for example compositions comprising pharmaceutically active compositions and agriculturally active compositions.

[0004] Agriculturally active ingredients like agricultural pesticides, including

insecticides, fungicides, herbicides, miticides and plant growth regulators as well as tank-mix adjuvants or fertilizers are generally produced in pure or highly concentrated form. However, they are to be used on agricultural operation sites in low concentration. To this end, they are usually formulated with other ingredients that enable easy dilution by the farm operator. The dilution is generally performed by mixing the agricultural concentrated formulation with water.

[0005] Two kinds of formulations represent the largest sales volumes which are emulsifiable concentrates (EC) and suspensions concentrates (SC). Such concentrated formulations are advantageous since they are easy to prepare, they have a high concentration in active material, a good stability, a high biological activity, and they are cheap. However, emulsifiable concentrates (which comprise an active agent dissolved in an organic solvent) need to use organic solvents like for example xylene, naphtalene and N-methylpyrrolidone which are potentially dangerous regarding environment and human health. In contrast, suspensions concentrates (which are stable suspensions of active agents in an aqueous liquid and are safe and easy to manipulate) are not sufficiently effective and not convenient for active agent which are sensible to water.

[0006] To solve these drawbacks a third type of formulation has been developed, namely oil dispersions. This type of formulation consists in a suspension of active material(s) in an apolar medium, generally an oily fluid intended to be diluted with water before use. WO 2013/043678 discloses some concentrate formulations that can be readily combined with pesticide to form an oil dispersion which subsequently may be diluted, in particular by a farm operator, with water to form the corresponding pesticide emulsion. These prior art formulations include as oily vehicle at least one vegetable oil alkyl ester.

[0007] WO 2016/142518 discloses concentrate formulations comprising at least 20 % by weight of at least one non-ionic surfactant chosen from

polyethylene glycol esters of fatty acids surfactants, relative to the total weight of the concentrate formulation, a liquid medium wholly or partly formed from at least one non esterified vegetable oil or mixtures thereof, at least one phyllosilicate, said phyllosilicate being present in a content of less than or equal to 5 % by weight relative to the total weight of the concentrate formulation and at least one activator of said phyllosilicate.

[0008] There is still a need for further formulations useful for the manufacture of agricultural or pharmaceutic! compositions suitable for use in various applications.

[0009] It was thus an object of the present invention to provide formulations

comprising surfactants, organic liquids and viscosifier with good

application properties.

[0010] This object is achieved by the formulations in accordance with claim 1.

[001 1] Preferred embodiments of the formulations in accordance with the present invention are set forth in the dependent claims and in the detailed specification hereinafter.

[0012] A further embodiment of the invention is directed to the use of the

formulations in accordance with the invention for the manufacture of pharmaceutical or agricultural compositions.

[0013] A still further embodiment of the invention relates to a method for

preventing or combatting diseases in animals, such as mammals, or for preventing or combatting infestation of plants by pests and/or of regulating plant growth, comprising the application of a mixture obtained by diluting a formulation according to the invention which additionally comprises a biologically active ingredient.

[0014] For the purpose of the present invention, the terms "emulsifiable

formulation" mean a formulation that forms an emulsion when diluted into water and mixed by inversion of the vial. Preferably, after 10 inversions of the vial (CIPAC MT36 and MT180) such emulsion is stable at least 30 minutes, and in particular two hours after its formation ("stable" meaning that no or only little phase separation of cream is observed)

[0015] The formulations in accordance with the invention comprise as component a) at least 3 wt%, based on the total weight of the formulation, of at least one surfactant S.

[0016] According to preferred embodiments the formulation comprises from 3 to 50, preferably from 5 to 40 and more preferably from 10 to 35 wt% of the surfactant S.

[0017] The surfactant S comprises at least two C2-C10 oxyalkylene units.

[0018] The surfactant S which is comprised in the invented formulation is free of aromatic ring.

[0019] More generally, the invented formulation is either free of any surfactant S^* comprising one or more aromatic rings (whatever alkoxylated or not), or comprises at least one surfactant S^* comprising one or more aromatic rings in an amount that does not exceed 10 wt.%, based on the total weight of surfactant S and surfactant S^*. Preferably, the invented formulation is either free of any surfactant S^* comprising one or more aromatic rings, or comprises at least one surfactant S^* comprising one or more aromatic rings in an amount that does not exceed 3 wt.%, based on the total weight of surfactant S and surfactant S^*. More preferably, the invented formulation is essentially free or is free of any surfactant S^* comprising one or more aromatic rings. Still more preferably, the invented formulation is free of any surfactant S^* comprising one or more aromatic rings. As herein used, the terms "aromatic rings" include aromatic rings (such as benzene ring) or heteroaromatic rings (such as furan ring). Besides, as herein used, the terms "aromatic rings" include aromatic rings that are available as single rings (such as benzene ring) and aromatic rings that are part of fused ring systems (such as naphthalene ring).

Accordingly, optional surfactants S^*1 comprising at least two C2-C10 oxyalkylene units but comprising one or more aromatic rings (such as nonylphenol ethoxylates) can only be incorporated in the invented formulation to the extent that their content in the formulation does not exceed 10 wt.%, based on the total weight of surfactant S and surfactant S^*. A fortiori, the same holds true for optional surfactants S^*2 which are free of oxyalkylene units and which comprise one or more aromatic rings (such as sodium dodecylbenzene sulfonate).

[0020] For the purpose of the present invention, the term "surfactant" means a compound that, when present in water, lowers the surface tension of water. Surfactants may act as detergents, wetting agents, surfactants, foaming agents, and dispersants.

[0021] Surfactants S can be generally grouped into ionic and non-ionic

representatives.

[0022] The surfactant S is advantageously selected from the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants and mixtures thereof.

[0023] The surfactant S is preferably selected from non-ionic surfactants and from mixtures of at least one non-ionic surfactant with at least one cationic surfactant, it being understood that the aforesaid non-ionic and cationic surfactants each comprise at least two C2-C10 oxyalkylene units and are free of any aromatic ring.

[0024] The surfactant S is more preferably is preferably selected from non-ionic surfactants.

[0025] For the avoidance of doubt, an oxyalkylene moiety (also referred to as

"alkylene oxide" moiety) is intended to denote a divalent moiety of formula -r-O- wherein r is alkylene. In the surfactant S in accordance with the present invention, r is C2-C10 alkylene. Divalent group r can be linear or branched. In the surfactant S, it is preferred that divalent group r is linear. Divalent group r is preferably a C2-C6 group, such as n-hexylene, n- pentylene, n-butylene, n-propylene or ethylene. It is more preferably selected from the group consisting of n-propylene (-CH2-CH2-CH2-), ethylene (-CH2-CH2-) and mixtures thereof. Still more preferably, it is ethylene, and the corresponding oxyalkylene moiety is known as ethylene oxide or oxyethylene (-CH2-CH2-O-).

[0026] The total number of oxyalkylene moieties in the surfactant S may vary to a large extent, and will be easily optimized by the skilled person depending on the chemical nature of the non-oxyalkylene moieties which the surfactant S may also comprise. The total number of oxyalkylene moieties in the surfactant S can be of at least 3, at least 4, at least 6, at least 8, at least 12, at least 16, at least 20, at least 50, at least 200 or at least 1000. Besides, the total number of oxyalkylene moieties in the surfactant S can be of at most 5000, at most 1000, at most 200, at most 50, at most 20, at most 16, at most 12 or at most 8. Any ranges of values for the total number of oxyalkylene moieties obtained by combining any above cited lower limit with any above cited upper limit should be considered as herein clearly and unambiguously described.

[0027] The surfactant S may contain from 0 up to at most 4, at most 3, at most 2 or at most 1 carbon atom(s) other than the carbon atoms contained in its oxyalkylene units -r-O- The surfactant S may be essentially free or completely free of carbon atoms other than the carbon atoms contained in its oxyalkylene units -r-O-. The hereinafter described poly(alkylene oxide)s often meet these features.

[0028] Alternatively, the surfactant S may further contain at least 6, at least 8, at least 10, at least 12, at least 14, at least 16, at least 18 or at least 20 carbon atoms other than the carbon atoms contained in its oxyalkylene units -r-O-; the hereinafter described emulsifiers often meet these features. In this case, the surfactant S may contain carbon atoms other than the carbon atoms contained in its oxyalkylene units -r-O- in an amount not exceeding 40, 30, 25, 20, 18 or 16 carbon atoms.

[0029] The surfactant S is advantageously free of ethylenic unsaturation. [0030] In some embodiments, the surfactant S is an ionic surfactant. Ionic surfactants can be characterized by the ionic nature of at least part of their hydrophilic moiety (possibly, all) their hydrophilic moiety(-ies). Ionic surfactants suitable as surfactants S are of mixed ionic-non ionic nature, in that they comprise at least one non ionic moiety (namely the oxyalkylene units) in addition to the at least one ionic moiety; said non ionic moiety is optionally directly connected to said ionic moiety.

[0031] When the surfactant S is anionic, the at least one hydrophilic ionic moiety is advantageously selected from the group consisting of sulfates (-O-SO3^"), sulfonates (-SO3^" ). carboxylates [C(=O)O- ] and mixtures thereof (as it is the case e.g. for sulfosuccinate-type surfactants).

[0032] There are other groups of anionic surfactants S known to the skilled

perosn and which have been decribed in the prior art. The skilled person will select the best suitable surfactant based on his professional

knowledge and the specific application case, so that no further details need to be given here.

[0033] As above said, the ionic surfactant S, which can be cationic or anionic, further includes at least one non-ionic hydrophilic moiety. Sometimes, the additional non ionic moiety is directly connected to an ionic moiety of the ionic surfactant S, and can therefore form a combination of hydrophilic moieties of mixed ionic-non ionic nature, such as in oxyalkylene sulfates of formula -O-A_y-SO3^" wherein A denotes an oxyalkylene unit (e.g.

CH2CH2O, CH2CH2CH2O or CH₂CH(CH₃)O or combinations thereof) and y ranges from 2 to 50.

[0034] The non ionic moiety consists generally of one or more C2-C10, preferably C2-C₄ oxyalkylene units, preferably oxyethylene and/or oxypropylene units, and more preferably oxyethylene units. The total number of oxyalkylene units in the ionic surfactant is in this case preferably of from 2 to 50, preferably of from 3 to 25 and even more preferably of from 4 to 12.

[0035] Exemplary representatives of alkoxylated ionic surfactants S are ether carboxylates of formula R-O-Ay-Ch -COOX wherein R is C8-C20 alkyl or C8-C20 alkenyl (such as oleyl), A is a C2-Ciooxyalkylene unit (e.g. CH2CH2O), X is ammonium or an alkali metal and y ranges from 2 to 50.

[0036] Other examples are ester carboxylates of a di-, tri- or tetracarboxylic acid, and are obtainable by the condensation reaction of an alcohol with the di-, tri- or tetracarboxylic acid (e.g. glycolic acid, citric acid or tetrabutane carboxylic acid), wherein the alcohol has been previously alkoxylated.

[0037] Further mentioning may be made of :

[0038] - ether sulfonates of formula R-O-A_y-CH₂-SO₃X wherein R is C₈-C₂o alkyl or C8-C20 alkenyl (such as oleyl), A is a C2-C10 oxyalkylene unit (e.g.

CH2CH2O), X is ammonium or an alkali metal and y ranges from 2 to 50,

[0039] - alkyl or alkenyl ether sulfates of formula R-O-A_y-SOsX wherein R is Cs- C20 alkyl or alkenyl (such as oleyl), A is a oxyalkylene unit

(e.g. -CH2CH2O-), X is ammonium or an alkali metal and y ranges from 2 to 50,

[0040] - alkoxylated sulfosuccinates, such as the alkoxylated sulfosuccinates of formula R-O-A_y-C(=O)-CH₂-CH(SO₃X)-C(=O)OX'

wherein R is C8-C20 alkyl or C8-C20 alkenyl (such as oleyl), A is a oxyalkylene unit (e.g. CH2CH2O), X and X' are independently ammonium or an alkali metal and y ranges from 2 to 50, and

[0041] - monoalkyl and dialkyl ether phosphates of respective formulae

R-O-Ay-P(=O)-(OX)₂ and (R-A_y)₂-O-P(=O)-OX, wherein R is C₈-C₂o alkyl or C8-C20 alkenyl (such as oleyl), A is a oxyalkylene unit (e.g. CH2CH2O), X is ammonium or an alkali metal and y ranges from 2 to 50.

[0042] As mentioned hereinabove, for the purpose of the present invention,

preferred or more surfactants S are or include a non-ionic surfactant, and same will now be described in some more detail.

[0043] Non-ionic surfactants S are advantageously selected from the group

consisting of ether-based non-ionic surfactants, ester-based non-ionic surfactants, amine-based non-ionic surfactants, amide-based non-ionic surfactants, fluoro-surfactants and mixtures thereof.

[0044] A first class of non-ionic surfactant S in accordance with the present

invention is constituted by so called "poly(alkylene oxide)s". Poly(alkylene oxide)s suitable for use in the present invention are polymers essentially all or all the repeating units of which comply with general formula -r-O- wherein r represents a divalent alkylene group having from 2 to 10 carbon atoms. Such poly(alkylene oxide)s may be terminated by a hydroxyl group. Particularly suitable poly(alkylene oxide)s are those wherein r has from 2 to 4 carbon atoms, preferably from 2 to 3 carbon atoms, more preferably 2 carbon atoms. The poly(alkylene oxide)s may be either linear or branched. Linear poly(alkylene oxides) are generally preferred.

[0045] Specific examples of suitable poly(alkylene oxide)s include

polyoxyalkylene polyols, such as polyoxyethylene glycol [also known as poly(ethylene glycol) or poly(ethylene oxide)], polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol [also commonly referred to as poly(propylene glycol) or poly(propylene oxide)], polyoxypropylene triol, polyoxypropylene tetraol, polyoxybutylene glycol, polyoxypentylene glycol, polyoxyhexylene glycol, polyoxyheptylene glycol, and

polyoxyoctylene glycol. These polymers may be used either individually or in combinations of two or more; for example, it can be cited random copolymers of ethylene oxide and propylene oxide, and poly(ethylene oxide)-poly(propylene oxide) block copolymers.

[0046] The hydroxyl end groups of the poly(alkylene oxide)s may according to a preferred embodiment be partly or fully substituted by alkoxide groups, preferably methoxy or alkoxy. Methods for converting hydroxyl groups of poly(alkylene oxide)s into alkoxy groups are known to the skilled man and described in the literature.

[0047] Certain suitable oxyalkylene-containing compounds suitable as surfactants S in the formulation in accordance with the instant invention are amine- terminated poly(alkylene oxide)s, in particular amine-terminated

poly(ethylene oxide)s or amine-terminated poly(propylene oxide)s, including copolymers comprising both mentioned types of oxyalkylene units which are commercially available under the tradename Jeffamine^® from Huntsman Chemical Corporation.

[0048] The molecular weight of the poly(alkylene oxide)s in accordance with this embodiment may cover a wide range as discussed above generally for surfactants S. In certain cases poly(alkylene oxide)s having a number average or weight average molecular weight of at least 20,000, preferably at least 200,000 and even more preferably at least 1 ,000,000 are advantageous. In other cases average molecular weights of at most 20,000, preferably at most 10,000 and even more preferably at most 1000 are useful. The molecular weight of the suitable poly(alkylene oxides) may also be optimized in view of the specific application case. For example, a methoxy-terminated poly(ethylene oxide) having a number average or a weight average molecular weight of at most 2,000 may be used.

Copolymers comprising oxyethylene and oxypropylene units in random or block distribution may also be suitable and respective products are commercially available under the tradename Pluronics^®from BASF.

[0049] Alternatively, the surfactant S can consist essentially of or consist of at least one hydrophilic block and at least one lipophilic block. The case being, the surfactant S comprises advantageously up to four hydrophilic first blocks and up to four lipophilic blocks. Possibly, the surfactant S comprises 1 or 2 hydrophilic first blocks and 1 or 2 lipophilic blocks. Many surfactants S in accordance with the present invention have one and only one hydrophilic first block and one and only one lipophilic block. Certain substances among such surfactants S may qualify as emulsifiers.

[0050] The surfactant S may be chosen from ether based alkoxylated non ionic surfactants. Ethers of carboxylic acids-based non-ionic surfactants, alcohol-based non-ionic surfactants, oside-based non-ionic surfactants and silicone non-ionic surfactants may be mentioned as examples of such surfactants.

[0051] Certain non-ionic surfactants S of interest are ethers of carboxylic acids having the following formula :

[0052] R¹⁰-O-(R -O)y-CH₂-COOH ,

[0053] wherein R ⁰ is C₈-C₂o alkyl or C₈-C₂o alkenyl, R is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50. [0054] In particular, ethers of carboxylic acids-based non-ionic surfactants are preferably represented by polyoxyethylene-based non-ionic surfactants, polyoxypropylene-based non-ionic surfactants, and polyoxyethylene- polyoxypropylene-based non-ionic surfactants. A polyoxyethylene-based non-ionic surfactant may be a polyoxyethylene alkyl ether or a

polyoxyethylene polyoxypropylene alkyl ether.

[0055] Among polyoxyethylene alkyl ethers, one may cite compounds such as polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene isostearyl ether.

[0056] Among polyoxyethylene-polyoxypropylene alkyl ethers, one may cite

compounds such as polyoxyethylene-polyoxypropylene cetyl ether and polyoxyethylene-polyoxypropylene decyltetradecyl ether.

[0057] Alcohol-based non-ionic surfactants of interest in accordance with the present invention may be represented by alkoxylated alcohols.

[0058] Within the scope of the present invention, the term "alkoxylated" relies upon the presence of oxyalkylene units, for which the total number of these units generally ranges from 2 to 50, preferably from 3 to 25, preferably from 4 to 12, preferably from 2 to 10, most preferably from 2 to 6 or, in accordance witn another embodiment, preferably from 10 to 50, most preferably from 10 to 35.

[0059] Alkoxylated alcohols of interest may be represented by a compound of the general formula as follows:

[0060] R2i-O-(R²²-O)y-H

[0061] wherein R² is C6-C30 alkyl or C6-C30 alkenyl, preferably C8-C20 alkyl or Cs- C20 alkenyl, more preferably lauryl or myristyl or palmityl, R²² is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.

[0062] Examples of alkoxylated alcohols suitable as a non-ionic surfactant S are the products of the condensation of (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide, such as ethylene oxide, with (ii) a mole of a saturated or unsaturated (preferably ethylenically unsaturated) fatty alcohol, especially a C8-C20 alcohol chosen from lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, oxoalcohols and mixtures thereof.

[0063] Alcoxylated alcohols may be commercially available under the tradenames Brij^® (Atlas Chemical Co.), Genapol^® (Clariant) and Lutensol^® (BASF).

[0064] Among ester-based non-ionic surfactants of interest as surfactants S, one may cite alkoxylated oils and fats. These compounds encompass ethoxylated and/or propoxylated derivatives of lanolin (wool fat) or of castor oil. Lanolin is the generic name of a wax containing a mixture of esters and polyesters of high-molecular-weight alcohols and fatty acids. Castor oil is a mixture of a triglyceride of fatty acids.

[0065] Other examples of ester-based non-ionic surfactants may be represented by alkoxylated acids, such as the compounds represented by monoesters and diesters.

[0066] Monoesters of interest as surfactants S may be represented by a

compound of the general formula as follows:

[0068] wherein R³ is C6-C30 alkyl or C6-C30 alkenyl, preferably C8-C20 alkyl or Cs- C20 alkenyl, R³² is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.

[0069] Examples of alkoxylated acid monoesters are the condensation products of from 2 to 50 moles (in particular, from 4 to 16 moles) of an alkylene oxide (such as ethylene oxide) with one mole of a saturated or

unsaturated fatty acid chosen from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mixtures therof.

[0070] An example thereof is Deplastol^® product which is a condensate of about 4-5 mol oxyethylene units with lauric acid and/or myristic acid (Cognis, Germany). Corresponding propoxylated and/or butylated fatty acids may also be included in the alkoxylated acids monoesters of interest. [0071] Diesters of interest may be represented by a compound of the general formula as follows

[0072] wherein R⁴ and R⁴³ are independently a C6-C30 alkyl or C6-C3o alkenyl, preferably a C8-C20 alkyl or C8-C20 alkenyl , R⁴² is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.

[0073] Other examples of ester-based non-ionic surfactants of interest may

represented by alkoxylated glycol, such as alkoxylated ethylene glycol esters and alkoxylated propylene glycol esters.

[0074] Alkoxylated ethylene glycol respectively propylene glycol esters may be represented by a compound of the general formula as follows

[0075] wherein R⁵ is C6-C30 alkyl or C6-C30 alkenyl, preferably C8-C20 alkyl or Cs- C20 alkenyl, R⁵² is hydrogen or methyl and R⁵³ is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2-, -CH₂-CH(CH₃)- or a mixture thereof, and y ranges from 2 to 50.

[0076] Alkoxylated esters of monoglycerides, dialkoxylated esters of diglycerides and trialkoxylated esters of triglycerides may also be compounds of interest, said esters being the reaction products of glycerol, or one of its derivatives, with a carboxylic acid comprising from 8 to 20 carbon atoms and comprise in total from 6 to 60 oxyalkylene units.

[0077] Among the non limitating ester-based non-ionic surfactants, one may cite polyoxyethylene alkylesters, polyoxyethylene glycerine aliphatic acid esters, polyoxyethylene castor oil, polyoxyethylene sorbitol aliphatic acid esters, polyethylene glycols aliphatic acid esters, polyoxyethylene sorbitan aliphatic esters, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene castor oil, polyoxyethylene cured castor oil, polyoxyethylene cured castor oil fatty acid ester, polyoxyalkylenated fatty acid esters, oxyalkylenated alkyl polyglycosides.

[0078] In particular, among polyoxyethylene glycerin fatty acid esters, one may cite polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monooleate, and polyoxyethylene glyceryl monoisostearate.

[0079] Among polyethylene glycol fatty acid esters, one may cite polyethylene glycol monostearate, polyethylene glycol monooleate and polyethylene glycol monolaurate.

[0080] Amine-based or amide based non-ionic surfactants are alo suitable and polyoxyethylene alkylamides or polyoxyethylene aliphatic acid amides may be mentioned in this regard.

[0081] Other examples of amide-based non-ionic surfactants of interest as

surfactants S in accordance with the present invention may be

represented by alkoxylated alkanolamides, such as alkoxylated

monoalkanolamides and dialkoxylated dialkanolamides, it being

undersood that the amide-based non-ionic surfactants of interest are all free of any aromatic ring.

[0082] Particularly preferred as surfactants in the formulations according to the invention are polyethylene glycol esters of fatty acids.

[0083] Representative thereof are polyethylene glycol fatty acid monoesters and polyethylene glycol fatty acid diesters, more typically mono- and di-esters of polyethylene glycols and saturated or unsaturated (C8-C22), more typically (C12-C18), fatty acids and mixtures thereof, such as for example, poly(ethylene glycol) monomyristates, poly(ethylene glycol)

monostearates, poly(ethylene glycol) distearates, poly(ethylene glycol) monooleates, poly(ethylene glycol) dioleates, poly(ethylene glycol) linolenates, poly(ethylene glycol) dibehenates, poly(ethylene glycol) monobehenates, poly(ethylene glycol) monoerucates, and their mixtures.

[0084] Examples of suitable polyethylene glycol esters of fatty acids are

commercialized by Solvay under the names Alkamuls^® AP, Alkamuls^® A, Alkamuls^® VO/2003 and Alkamuls^® VO2005.

[0085] Alkamuls^® VO/2003 and Alkamuls^® VO2005 are particularly preferred according to the present invention.

[0086] The specific surfactant S used according to the invention contributes to the obtention of a pourable formulation, and facilitates emulsification when the formulation is placed in the presence of water. It also provides stabilization over time of the so-formed emulsion by limiting, or even avoiding, phase separation.

[0087] As component b) the formulations according to the invention comprise an organic liquid or, more generally, an organic liquid medium. For the purpose of the present invention, "liquid medium" means a medium that is in the liquid phase at room temperature and a pressure of one

atmosphere.

[0088] The choice of organic liquid is not subject to particular limitations and the skilled person will select a suitable organic solvent based on his

professional expertise and the specific application case so that no furher details need to be given here. Suitable organic liquids have been described in the literature and are commercially available.

[0089] According to an embodiment, the organic liquid used in the formulation according to the invention is a good solvent and can be a polar solvent or a mixture of a polar solvent and an apolar solvent.

[0090] Just by way of example, alcohols having from 1 to 10 carbon atoms, preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol or ethylhexanol may be mentioned here.

[0091] Another group or organic liquids which may be mentioned, areacetal

derivatives having from 2 to 12 carbon atoms, and is preferably selected from the Augeo^® family of solvents (available from Solvay SA) such as Augeo^® SL191 which is a racemic mixture of (+/-)-2,2-dimethyl-4- hydroxymethyl-1 ,3-dioxolane also known as isopropylidene glycerol.

[0092] Further examples are selected from alkyl esters having from 2 to 12

carbon atoms, preferably selected from ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, octyl acetate or from mixtures of (i) alcohols having from 1 to 10 carbon atoms (preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol, ethylhexanol), (ii) alkyl esters having from 2 to 12 carbon atoms (preferably selected from ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, octyl acetate) and (iii) acetal derivatives having from 2 to 12 carbon atoms (preferably selected from the Augeo^® family of solvents (available from Solvay SA) such as Augeo^® SL191 which is a racemic mixture (+/-)-2,2-dimethyl-4-hydroxymethyl-1 ,3-dioxolane, also known as isopropylidene glycerol).

[0093] Also mentioned here maybe esterified or non esterified mineral oils,

vegetable oils, animal oils or synthetic oils.

[0094] Preferred organic liquids as component b) are non-esterified vegetable oils or mixtures thereof.

[0095] For the purpose of the present invention, "non-esterified vegetable oil" means a native vegetable oil that is chemically not transformed and in particular not esterified. In other words, it is equivalent to its natural form. Within the context of the present invention non-esterified vegetable oils are understood to be triglycerides or mixtures of triglycerides.

[0096] More particularly, this vegetable oil or mixtures thereof constitutes the

liquid phase of the formulation and is dedicated to vehicle at least the surfactant S and the viscosifier.

[0097] These vegetable oils may be selected for example from the group

consisting of soybean oil, corn oil, cottonseed oil, sunflower oil, maize oil, rice oil, olive oil, linseed oil, rapeseed oil, canola oil, palm oil, coconut oil and mixtures thereof.

[0098] Rapeseed oil, canola oil, soybean oil and corn oil are particularly

convenient for the invention. [0099] The formulation according to the invention may preferably contain from 10 to 90 % by weight, for instance from 40 to 85 % by weight, in particular from 40 to 80 % by weight, for instance from 50 to 75 % by weight relative to its total weight, of at least one organic liquid as component b), and in particular of a non-esterified vegetable oil or mixtures thereof.

[00100] The formulations according to the invention comprise as component c) at least 0.1 wt% of at least one viscosifier selected from N- hydrocarbyldiamides of general formula (I)

wherein

R^a or R^b is selected from hydrogen or a linear, branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms, with the proviso that either R^a or R^b is hydrogen,

R^c is a cyclic or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 2 to 25 carbon atoms.

[00101] In accordance with a preferred embodiment of the invention, the viscosifier is a N-hydrocarbyldiamide composition comprising

c1 ) at least one compound of formula (la)

wherein

R¹ is selected from linear or branched or cyclic, saturated or unsaturated, hydrocarbon chains having from 1 to 40 carbon atoms,

R² is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chains having from 1 to 15 carbon atoms, and R³ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms, and

c2) at least one compound of formula (lb)

wherein

R⁴ is selected from linear or branched or cyclic, saturated or unsaturated, hydrocarbon chains having from 1 to 40 carbon atoms,

R⁵ is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chains having from 1 to 15 carbon atoms, and

R⁶ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms.

[00102] In the compounds of formula (I) R^a or R^b is selected from hydrogen or a linear, branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms, with the proviso that one and only one of R^a or R^b is hydrogen.

[00103] R^c in formula (I) is a cyclic or branched, saturated or unsaturated,

hydrocarbon aliphatic chain having from 2 to 25 carbon atoms.

[00104] Within the meaning of the present invention, the term "hydrocarbon chain", is to be understood as a hydrocarbon chain comprising carbon atoms and hydrogen atoms, wherein said hydrocarbon chain may optionally be substituted by one or more heteroatoms, such as oxygen atoms.

[00105] The term "aliphatic chain", is to be understood as a non-aromatic chain.

[00106] According to an embodiment of the invention, R^a or R^b of the compound of formula (I) is a hydrocarbon chain constituted only by carbon atoms and hydrogen atoms.

[00107] According to an embodiment of the invention, R^a or R^b of the compound of formula (I) is aromatic. In particular, R^a or R^b may be selected from phenyl or furyl groups. [00108] According to another embodiment of the invention, R^a or R^b of the compound of formula (I) is a linear, branched or cyclic aliphatic (non- aromatic) hydrocarbon chain.

[00109] According to an embodiment of the invention, R^a or R^b is selected from a linear or branched, saturated or unsaturated, hydrocarbon chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[001 10] According to an embodiment of the invention, R^a or R^b is selected from a linear, unbranched, saturated or unsaturated, hydrocarbon aliphatic chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[001 1 1] According to an embodiment of the invention, R^a or R^b is selected from a linear unbranched saturated hydrocarbon aliphatic chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[001 12] According to an embodiment of the invention R^a or R^b is selected from pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, palmityl, stearyl, 12-hydroxy stearyl, oleyl, 12-hydroxyloleyl, linoleyl, linolenyl, arachidyl, behenyl or erucyl groups.

[001 13] According to an embodiment of the invention, R^c is not cyclic. Preferably, R^c is selected from hydrocarbon aliphatic chains comprising a hydrocarbon main chain having from 1 to 14 carbon atoms and a side chain having from 1 to 6 carbon atoms. Preferably, R^c is selected from hydrocarbon aliphatic chains comprising a hydrocarbon main chain having from 2 to 8 carbon atoms and a side chain having from 1 to 4 carbon atoms.

[001 14] According to an embodiment of the invention, R is selected

from -CH(CH₃)-CH₂-; -CH₂-CH(CH₃)- ; -CH(CH₃)-CH₂-CH₂- ; -CH(CH₂- CH₃)-CH₂- and -CH₂-CH₂-CH(CH₃)-. [001 15] Preferably, the compounds of formula (I) according to the invention do not present urea functions of type -NH-CO-NH-.

[001 16] If the viscosifier is a N-hydrocarbyldiamide composition comprising

compounds of formula (la) and (lb), the molar ratio of the compound of formula (la) to compound (lb) is preferably in the range of from 70:30 to 99: 1 , preferably in the range of from 75:25 to 98:2, more preferably of from 85: 15 to 97:3 and most preferably of from 90:10 to 97:3.

[001 17] In the N-hydrocarbyldiamide composition used as viscosifier, the

aggregated weight proportion of compounds (la) and (lb) is preferably at least 50 wt%, further preferably at least 80 wt%, more preferably at least 90 wt% of the total weight of the composition. Even more preferably the N- hydrocarbyldiamide composition essentially consists of compounds (ia) and (lb) or consists of compounds (la) and (lb).

[001 18] Preferred in accordance with the invention as viscosifiers are N- hydrocarbyldiamide compositions in which R is identical to R⁴, R² is identical to R⁵ and R³ is identical to R⁶, i.e. the N-hydrocarbyldiamide composition is preferably an isomer mixture.

[001 19] According to an embodiment of the invention, R¹ or R⁴ of the compound of formula (la) respectively formula (lb) is a hydrocarbon chain constituted only of carbon atoms and hydrogen atoms.

[00120] According to another embodiment of the invention, R¹ or R⁴ of the

compound of formula (la) respectively formula (lb) is a linear, branched or cyclic aliphatic (non-aromatic) hydrocarbon chain.

[00121] According to an embodiment of the invention, R or R⁴ is selected from a linear or branched, saturated or unsaturated, hydrocarbon chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[00122] Just by way of example, R¹ and/or R⁴ can preferably be selected from

pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, palmityl, stearyl, 12-hydroxy stearyl, oleyl, 12-hydroxyloleyl, linoleyl, linolenyl, arachidyl, behenyl or erucylgroups. [00123] R² and/or R⁵ are preferably selected from hydrocarbon aliphatic chains comprising a hydrocarbon main chain having from 1 to 14 carbon atoms. R² and/or R⁵ preferably comprise from 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms and still more preferably 1 to 2 carbon atoms

[00124] Besides, R² and/or R⁵ are preferably selected from (i) linear alkylene

chains and (ii) from linear alkylene chains substitued by one and only one linear alkyl group, wherein the linear alkyl group substituent comprises a number of carbon atoms that is preferably lower, more preferably does not comprise more than half of the carbon atoms of the linear alkylene chains and more preferably does not exceed two and more preferably does not exceed one carbon atom. More preferably, R² and/or R⁵ are linear alkylene chains.

[00125] Most preferably, R² and/or R⁵ are methylene.

[00126] Other possible choices for R² and/or R⁵ include

-(CH₂)i-, wherein I is 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 1 or 2

-CH(CH₃)-(CH₂)j- wherein j is 1 , 2, 3, 4, 5, 6, 7, 8 or 9, preferably 1 or 2 and

-(CH2)k-C(CH3)-(CH2)k'- wherein k and k' are integers equal to or exceeding 1 and the sum of k and k' is 2, 3, 4, 5, 6, 7, 8, or 9.

[00127] R² and R⁵ may also be; -CH(CH₂-CH₃)-CH₂-.

[00128] R³ and R⁶ are linear or branched alkyl groups with 1 to 8, preferably 1 to 4 carbon atoms, most preferably R³ and R⁶ are methyl.

[00129] Preferably, the compounds of formula (la) and (lb) forming the N- hydrocarbyldiamide mixture according to the invention do not present urea functions of type -NH-CO-NH-.

[00130] The compounds of formula (I) or the mixtures consisting of the compounds of formula (la) and (lb) may be obtained by a process wherein at least one amine and at least one reactant selected from an imide, a diacid, a diester, a primary diamide, an ester amide, an acid ester or other combinations are reacted. [00131] A preferred process for manufacturing the N-hydrocarbyldiamide mixtures of compounds (la) and (lb) comprises the steps of

a) the reaction between an amine and a reactant selected from an imide, a diacid, a diester, a primary diamide, an ester amide or an acid ester, and thereafter

b) subjecting the reaction product obtained in step a) to at least two cycles of recrystallization and washing steps. With increasing number of recrystallization cycles, the ratio of compounds of formula (la) and (lb) increases, if (la) and (lb) are isomers of the same N-hydrocarbyldiamide.

[00132] Ammonia may also be added during the process if it is not already present in the molecule as amide or imide functions. Ammonia may allow favoring the manufacture of the mono-alkyl form (versus the dialkyl form) of the diamide and may also allow favoring the elimination of by-products formed during the reaction (such as alcohol coming from reaction with ester as a co-product).

[00133] General processes for manufacturing diamides are described in WO

2010/031867.

[00134] In particular, the process for manuifacture of the viscosifier comprises the direct reaction between a cyclic imide and an amine.

[00135] The compounds of formula (I), (la) and/or (lb) can thus be obtained by an imide ring-opening reaction of the cyclic imide with addition of the amine.

[00136] The imide may be preferably selected from 2-methyl-glutarimide, 3-methyl- glutarimide, 2-ethyl-glutarimide, 3-ethyl-glutarimide, 2-methyl-succinimide and 2-ethyl-succinimide.

[00137] For example, in order to obtain a compound of formula (la) or (lb) wherein

R² respectively R⁵ is -CH2-, then the imide can be a cyclic imide of formula (III-1 ):

[00138]

[00139] The amine is preferably a primary amine of general formula R¹'-NH2, with R defined as above.

[00140] The reaction for preparing the viscosifier may be performed for example, at a temperature ranging from 20°C to 200°C, preferably from 50°C to 180°C, more preferably from 100°C to 160°C. In the case of lighter amines, such as amines having less than 6 carbon atoms, the reaction may be performed with a progressive heating in order to avoid loss of amines through evaporation or may be performed under pressure to keep the amine in the liquid phase. For example, at the beginning of the reaction, the temperature of the mixture (ingredients) is approximately equal to the boiling point of the amine.

[00141] The reaction for preparing the viscosifier is preferably performed under atmospheric pressure.

[00142] The viscosifier used as component c) in the formulations according to the invention may be partially or fully solubilized in the organic liquid (solvent). It is preferably fully solubilized in the organic liquid (solvent).

[00143] The viscosifier used as component c) in the formulations according to the invention may be available in the form of a mixture M comprising the N- hydrocarbyldiamide (I), in particular (la) and (lb), and at least one solvent, said compound of formula (I) respectively the mixture of (la) and (lb) being partially or fully solubilized in said solvent.

[00144] In such mixtures M, the N-hydrocarbyldiamide compounds (I) or (la) and (lb) are preferably fully solubilized in the at least one solvent.

[00145] The mixture M is preferably a solution comprising at least one solvent and, fully dissolved therein, at least one compound of formula (I) or the compounds of formula (la) and (lb), that is to say the mixture M is free of any compound that would be insolubilized in the solvent.

[00146] Preferably, the mixture M is one which, when at room temperature and at atmospheric pressure (20 °C, 1 atm), comprises the N- hydrocarbyldiamides (I) or (la) and (lb) in partially or fully solubilized form in the solvent. More preferably, the mixture M is one which, when at room temperature and at atmospheric pressure, comprises the N- hydrocarbyldiamides of formula (I) or the mixture of (la) and (lb) in fully solubilized form.

[00147] Advantageously, the mixture M is one which, when at 60°C and at

atmospheric pressure, comprises the N-hydrocarbyldiamides (I) or (la) and (lb) in fully solubilized form in the solvent. Preferably, the mixture M is one which, when at 40°C and at atmospheric pressure, comprises the N- hydrocarbyldiamides (I) or (la) and (lb) in fully solubilized form.

[00148] Advantageously, the mixture M is a solution when it is put at 60°C and at atmospheric pressure. Preferably, the mixture M is a solution when it is put at 40°C and at atmospheric pressure. More preferably, the mixture M is a solution when it is put at room temperature (20°C) and at atmospheric pressure.

[00149] According to an embodiment, the solvent used in the mixture M is a good solvent and can be a polar solvent or a mixture of a polar solvent and an apolar solvent. Within the meaning of the present invention, by "polar solvents", it is to be understood solvents having a polar and hydrogen bonding components respectively δ_ρ and 5h (Hansen solubility parameter) strictly greater than 0. Hansen solubility parameters are well known for the skilled person: δ_ρ corresponds to the energy from dipolar intermolecular forces between molecules and 5h corresponds to the energy from hydrogen bonds between molecules.

[00150] According to an embodiment of the invention, the solvent of the mixture M is selected from alcohols having from 1 to 10 carbon atoms, preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol.

[00151 ] According to an embodiment of the invention, the solvent of the mixture M is selected from acetal derivatives having from 2 to 12 carbon atoms, and is preferably selected from the Augeo® family of solvents (available from Solvay SA) such as Augeo® SL191 which is a racemic mixture (+/-)-2,2- dimethyl-4-hydroxymethyl-1 ,3-dioxolane also known as isopropylidene glycerol. [00152] According to an embodiment of the invention, the solvent of the mixture M is itself a mixture of (i) alcohols having from 1 to 10 carbon atoms

(preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol), (ii) alkyl esters having from 2 to 12 carbon atoms (preferably selected from ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, ethylhexyl acetate or octyl acetate) and (iii) acetal derivatives having from 2 to 12 carbon atoms (preferably selected from the Solvay available Augeo family of solvents (available from Solvay SA) such as Augeo® SL191 which is a racemic mixture (+/-)-2,2-dimethyl-4-hydroxymethyl-1 ,3-dioxolane also known as isopropylidene glycerol).

[00153] According to an embodiment of the invention, the solvent of the mixture M is selected from lactate esters, in particular selected from methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, 2-ethylhexyl lactate, especially from methyl L-lactate, ethyl L-lactate, n-propyl L-lactate, n-butyl L-lactate, 2-ethylhexyl L-lactate.

[00154] The mixture M may be from a liquid state to a flowable thick paste at

temperatures ranging from 20°C to 50°C.

[00155] According to an embodiment of the invention, the N-hydrocarbyldiamide compound I respectively the mixture of N-hydrocarbyldiamines of formula (la) and (lb) in accordance with a preferred embodiment represents from 1 % to 75% by weight, preferably from 10% to 50% by weight, more preferably from 15% to 30% by weight, of the total weight of the mixture M.

[00156] According to a particular embodiment, the mixture M comprises

compounds (la) and (lb), wherein R and R⁴ differ in chain length. When the mixture M comprises such combination, the use of the mixture M is more flexible and can be used in very different carriers in order to allow the gelification of said carriers.

[00157] The mixture M may be obtained by simple mixing of the ingredients (N- hydrocarbyldiamide compounds and solvent), preferably at a temperature comprised between 10°C and 60°C, ideally about 25°C (room

temperature). [00158] The formulations according to the invention, in a preferred embodiment, comprise as component d) at least one biologically active ingredient, preferably a pharmaceutically active ingredient or an agriculturally active ingredient. The amount thereof is usually at least 0,5 wt%, preferably of form 1 -20 wt%, even more preferably of from 2 to 15 wt% of the weight of the formulation.

[00159] The term "biologically active ingredient", when used herein, is intended to denote an entity which interacts with biological material in a manner that dieseases in animals, such as mammals, may be prevented or combatted or which influences growth of agricultural crops or which combats weeds, insects, bacteria or fungi in agricultural crops.

[00160] In accordance with a preferred embodiment, the formulation comprises an agriculturally active ingredient selected from the group consisiting of agriculturally active ingredient is selected from herbicides, insecticides, fungicides, parasiticides, plant growth regulators, fertilizers, bactericides and insect repellents.

[00161] Biologically active ingredients have been described in the literature in

great variety and the skilled person will select the appropriate active ingredient based on his professional knowledge and taking into account the individual case of application. No further details need to be given here.

[00162] There is no principal limitation as to the nature of the biologically active ingredient in the formulation of the present invention.

[00163] For the purpose of the invention the biologically active compounds are preferably biologically active compounds used to control agricultural pests and include, for example, herbicides, plant growth regulators, crop dessicants, fungicides, bacteriocides, bacteriostats, insecticides, and insect repellants.

[00164] Naturally, the formulation according to the invention may further contain any additive usually contemplated in phytosanitary formulations like for example safeners. [00165] APPLICATIONS

[00166] The preferred application for the formulations according to the invention is for the manufacture of agricultural formulations, for which now certain advantages which may be achieved are described in more detail.

[00167] The formulations according to the invention allow to achieve stabilized oil dispersions or emulsions with a great diversity of salts and/or active materials, in particular active compounds used to control agricultural pests. However, these concentrate formulations may also be convenient for vehiculing other active materials like fertilizers. These active materials and/or salts may be of very different chemical nature, like for example organic, inorganic, liposoluble or not.

[00168] The concentrate formulations may be highlighted in many ways.

[00169] Firstly, they may be used as final oil dispersions that are directly prepared by the farm operators by dilution of the concentrates with water and optionally by addition of some additives.

[00170] Moreover, they may be used by industrial firms as vehicles for a plurality of agricultural, e.g. pesticidal active materials.

[00171] Thus, the farm operators may prepare pulverizable liquid compositions and in particular aqueous emulsions or suspoemulsions by diluting a concentrate according to the invention. Generally, they just proceed to a dilution with water and oil if necessary, and optionally also supplement the so-obtained pulverizable formulation with at least one ingredient chosen from salts, hydrocolloids and their mixtures. Of course, it is also possible for a concentrate formulation according to the invention to already contain such a material.

[00172] More particularly, the salts may be chosen among sodium carbonate,

sodium bicarbonate, ammonium sulfate and their mixtures.

[00173] As hydrocolloid particularly convenient for the invention, may be cited the guar.

[00174] Thus, a formulation according to the invention may be used by the farm operators for preparing different pulverizable compositions which may be kept for a long time without any undesirable phenomenon of demixtion. [00175] The non-aqueous formulations supplemented with at least one ingredient chosen from salts like sodium carbonate, sodium bicarbonate, ammonium sulfate or their mixtures; hydrocolloids such as guar; and their mixtures as well as the corresponding emulsions obtained by a dilution of the concentrates into water, are also known under the name of tankmix.

[00176] A tankmix may be obtained by adding to a formulation according to the invention prepared as above mentioned, at least an ingredient chosen from salts, hydrocolloids and their mixtures to a homogenizer. The so obtained composition is then blended and diluted or not with water to form an emulsion.

[00177] Thus, according to a specific embodiment a tankmix according to the

invention contains less than 2 % by weight of water and preferably is anhydrous.

[00178] Tankmix formulations according to the invention are pourable, show a good storage stability, are emulsifiable and provide stable emulsions when diluted into water.

[00179] The formulation according to the invention is also particularly interesting for industrial firms which, by using only one concentrate, may prepare a great diversity of pesticidal oil dispersions.

[00180] In particular, a pesticidal oil dispersion according to the invention may contain until 50 % in particular from 1 to 20 %, more preferably 3 to 10 % by weight of solid pesticidal active material(s) with respect to its total weight.

[00181] The particle size of such active materials preferably is lower than 50 μηη in particular lower than 20 μηη and more particularly lower than 10 μηη. This size may be measured by laser diffraction (CIPAC MT 187) or rough estimation of average diameter by optical microscopy.

[00182] Preferred agriculturally active materials for use in the formulations

according to the invention are abamectin, azamethiphos, azoxystrobin, cyproconazole, bordeaux mixture, carbendazim, chlorsulfuron, copper hydroxide, copper oxide, copper oxychloride, cymoxanil, diflubenzuron, PMP, ethofumesate, DMP, lenacil, fenoxaprop-p-ethyl, iodosulfuron, florasulam, flutriafol, imidacloprid, imidacloprid, b-cyfluthrin, indoxacarb, iprodione, isoproturon, mancozeb, copper oxy, metamitron, nicosulfuron, rimsulfuron, thiacloprid, deltamethrin, thiobendazole, uniconazole, difenconazole, oxyfluorfen, quizalofop-p-ethyl, tebuconazole and their mixtures.

[00183] It has to be noticed that the formulations according to the invention keep their storage stability when containing the active materials active materials.

[00184] Pesticidal oil dispersions obtained with the formulations according to the invention are still pourable. In particular, they preferably have a viscosity ranging from 500 to 3000 mPas.

[00185] The formulations of the inventions are particularly suitable for the

manufacture of compositions containing active ingredients where the active ingredients or e.g. adjuvants have to be suspended as particulate matter. Particulate matter for the purpose of the present invention is intended to denote any particles with different densities equal or different from the continuous medium. If the density is different from the density of the continuous medium, the latter should have a non zero yield stress value, preferably a yield stress value above 0.5 Pa and preferably above 0.75 Pa.

[00186] A formulation according to the invention may be obtained by adding, in the order listed, a non-esterified vegetable oil as organic liquid, a viscosifier as defined in the claims, a surfactant S as defined in the claims and, optionally, an active ingredient according to the invention to a

homogenizer, and blending the ingredients after each addition.

[00187] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence. [00188] (EXAMPLES

[00189] Example 1

[00190] Preparation of a N-hexyldiamide compound (also named hereafter C6 gelator 65/35)

[00191] C6 Gelator lsomer-4/lsomer-2 Ratio 65/35

[00192] In a 500 ml glass reactor equipped with a cooling system, 100.0 g of methyl glutarimide (MGI) and 76.6 g of hexylamine and then 1.0 g of tBuONa was added. The reactor was then heated to 130°C and maintained at the reaction temperature for 2.5h. Then the reaction mixture was cooled down. The solid was added into 400 ml of methylethylketone (MEK) and heated to 100°C. The solution was then cooled down and the obtained solid was collected by filtration and washed with ethyl acetate (EA , 2^*300ml). The obtained solid was dried in vacuo to give 137.0 g of white solid, the yield was 76%, the purity was >98%.

[00193] NMR analysis showed that the product was a mixture of 2 isomers:

- N -hexyl-4-methylpentanediamide (65 wt%),

- N¹-hexyl-2-methylpentanediamide (35 wt%).

[00194] Preparations of formulations according to the invention

[00195] All formulations were prepared in 8 to 20ml scintillation glass vials.

Appropriate weights of the gelator powder and the oils or solvents were weighted on a microbalance. Total weights of gelators plus liquid oil or solvent were from 3 to 18g.

[00196] Good dispersions and solubilizations of the gelators at high temperatures (90°C to 1 10°C) were obtained using a tip sonicator (Branson Sonifier® 450) 6.3 mm diameter tip at a duty cycle set at 50%, power at 70%, with sonication durations set at 4 minutes. All samples were fluid, transparent and clear at end of the sonicating preparation.

[00197] Unless specifically mentioned otherwise all samples were left to cool back to room temperature on a bench. The qualitative visual verification of the gelation was done by simply upturning the vials. The gelation was considered successful if no flow was observed upon inverting the vial at room temperature. [00198] The gelation process and gel strength of the samples were followed and quantified by the measurement of the gel's elastic modulus. Once sonicated the samples were introduced into the cup of a conical cylinder geometry in Ultra+ Kinexus® Rheometer from Malvern equipped with a temperature control unit. The samples were melted at 120°C under shear set at 100s-1 immediately followed by a oscillatory collection of elastic modulus G' versus time (frequency of 1 Hz at a 0.1 % strain) as the temperature was quenched from 120°C to 25°C then remaining at 25°C using the Peltier temperature controlled stage.

[00199] (Example 2

[00200] Rapeseed oil formulation

[00201] Gels were prepared with 0.75 wt%, 1.0 wt% and 2 wt% of C6 Gelator

(65/35) obtained in Example 1 in Rapeseed oil RADIA 6105 from Oleon and amounts varying from 0 to 40 wt% of the nonionic surfactant Alkamuls VO2003 (polyoxethylated fatty acid ester) from Solvay. The obtained gels were transparent and resisted to an upside-down flip of the vial.

[00202] (Example 3

[00203] Rapeseed oil formulation

[00204] A gel was prepared with 0.75 wt% of C6 Gelator (65/35) from example 1 in Rapeseed oil RADIA 6105 from Oleon and 30 wt% of the nonionic surfactant Alkamuls VO2003 from Solvay. The obtained gel was transparent and resisted to an upside-down flip of the vial. Upon injection in water with a 50 times or more dilution ratio good immediate "blooming" self-emu Isification was observed.

[00205] (Example 4

[00206] Methylated rapeseed oil formulation

[00207] A gel was prepared with 0.75 wt% of C6 Gelator (65/35) from example 1 in methylated rapeseed oil RADIA 7956 from Oleon and 30 wt% of the nonionic surfactant Alkamuls T85V from Solvay. The obtained gel was transparent and resisted to an upside-down flip of the vial. Upon injection in water with a 50 times or more dilution ratio good immediate "blooming" self-emulsification was observed. [00208] (Example 5

[00209] Pesticidal compositions in Rapeseed Oil

[00210] A formulation 1 was prepared with Rapeseed oil RADIA 6105 from Oleon, 0.75 wt% of the C6 gelator (65/35) from example 1 and 30wt% of the nonionic surfactant Alkamuls VO 2003 from Solvay. Then 4 wt% of Nicosulfuron was added to the formulation. The obtained pesticidal formulation was stable against sedimentation and presented no or very little syneresis upon storage at 45°C. The sample displayed good shear thinning behavior when subjected to a steady shear in a rheometer compatible with an easy pour from a container when shaken.

[0021 1] Upon injection in water with a 50 times or more dilution ratio good

immediate "blooming" self-emu Isification is observed.

[00212] [Example 6

[00213] Pesticidal compositions in methylated rapeseed oil

[00214] A formulation 2 was prepared with methylated Rapeseed oil RADIA 7956 from Oleon, 0.75wt% of the C6 gelator (65/35) from example 1 and 30wt% of the nonionic surfactant Alkamuls T85V from Solvay. 4 wt% of

Nicosulfuron was added to the formulation. The obtained pesticidal formulation was stable against sedimentation and presented no or very little syneresis upon storage at 45°C. The sample displayed good shear thinning behavior when subjected to a steady shear in a rheometer compatible with an easy pour from a container when shaken.

[00215] Upon injection in water with a 50 times or more dilution ratio good

immediate "blooming" self-emu Isification was observed.

[00216] [Example 7

[00217] A mixture M was prepared by weighing the C6 gelator (65/35) from

example 1 in n-Propyl L-lactate (Purasolv NPL from Corbion) to obtain a 25wt% solution and placing it in an oven at 60°C for complete dissolution.

[00218] For the following examples all performance tests were performed as

follows: [00219] Blooming tests were conducted according to the Cipac MT36.3 method listed in the CIPAC (Collaborative International Pesticide Analytical Council Guide lines) published in the CIPAC Handbook J 2000 on a ¼ reduced scale and all measurements were conducted diluting 2% in volume of the Oil Dispersion into 98% CIPAC D water at 30°C, after 10 inversions, the test tubes were maintained in a 30°C oven. Observations were made after 2hours using digital cameras image capture and image treatment to quantify creaming and sedimentation.

[00220] Viscosity measurements were made using a Gilson Viscoman.

[00221] Stability measurements were conducted by placing the formulations in a 40°C oven and capturing the image of each formulation after the storage time at 40°C indicated in each example.

[00222] [Example 8

[00223] Pesticidal compositions in rapeseed oil

[00224] A composition A1 was prepared in Rapeseed oil RADIA 6105 from Oleon and adding Mesotrione powder, the nonionic surfactant Alkamuls VO2003 from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture M from example 7 previously heated to 60°C is then introduced to the composition A1 to form the formulation B1. The formulation B1 is as follows: Mesotrione (1 OOg/l), Alkamuls VO 2003 7wt%, C6 Gelator 0.65wt%, n-Propyl L-lactate 1.95w% the rest being rapeseed oil. After a hand mixing at room temperature, the formulation B1 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00225] The results of performance tests are the following:

Blooming: 1.7 % Creaming and 0.5 % Sedimentation

Viscosity: 300-500cps

Stability: No Syneresis after 8 Weeks at 40°C

[00226] (Example 9

[00227] Pesticidal compositions in methylated rapeseed oil

[00228] A composition A2 was prepared in methylated Rapeseed oil RADIA 7956 from Oleon and adding Mesotrione powder, the nonionic Alkamuls T85V from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture M from example 7 previously heated to 60°C is then introduced to the composition A2 to form the formulation B2. The formulation B2 is as follows: Mesotrione (1 OOg/l), Alkamuls T85V 7wt%, C6 Gelator 1.2wt%, n-Propyl L-lactate 3.6w% the rest being methylated rapeseed oil. After a hand mixing at room

temperature, the formulation B2 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00229] The results of performance tests are the following:

Blooming: 1.8% creaming and 0.3% Sedimentation

Viscosity: 300-500cps

Stability: 7% Syneresis after 8weeks at 40°C

[00230] (Example 10

[00231 ] Pesticidal compositions in Soy Bean oil

[00232] A composition A3 was prepared in Soy Bean Oil Amesolv SOR Soybean oil from Ametech and adding Mesotrione powder, the nonionic surfactant Alkamuls VO2003 from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture M from example 7 previously heated to 60°C is then introduced to the composition A3 to form the formulation B3. The formulation B3 is as follows:

Mesotrione (100g/l), Alkamuls VO 2003 7wt%, C6 Gelator 0.65wt%, n- Propyl L-lactate 1.95w% the rest being Soy Bean oil. After a hand mixing at room temperature, the formulation B3 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00233] The results of performance tests are the following:

Blooming: 2.58% Creaming 0.58% Sedimentation

Viscosity: 300-500 cps

Stability: No Syneresis after 8 weeks at 40°C

[00234] (Example 11

[00235] Pesticidal compositions in Methyl Soyate/

[00236] A composition A4 was prepared in Methyl Soyate Amesolv MTES from

Ametch and adding Mesotrione powder, the nonionic surfactant Alkamuls T85V from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture M from example 7 previously heated to 60°C is then introduced to the composition A4 to form the formulation B4. The formulation B4 is as follows: Mesotrione (1 OOg/l), Alkamuls T85V 7wt%, C6 Gelator 1.2wt%, n-Propyl L-lactate 3.6w% the rest being Methyl Soyate. After a hand mixing at room temperature, the formulation B4 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00237] The results of performance tests are the following:

Blooming: 1.2% Creaming 0.3% Sedimentation

Viscosity: 300-500 cps

Stability: 8% Syneresis after 8 weeks at 40°C

[00238] (Example 12

[00239] Pesticidal compositions in rapeseed oil

[00240] A composition A5 was prepared in Rapeseed oil RADIA 6105 from Oleon and adding Nicosulfuron powder, the nonionic surfactant Alkamuls

VO2003 from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N- 5G medium speed) for 1.5 minutes. The mixture M from example 7 previously heated to 60°C is then introduced to the composition A5 to form the formulation B5. The formulation B5 is as follows: Nicosulfuron (100g/l), Alkamuls VO 2003 7wt%, C6 Gelator 0.65wt%, n-Propyl L-lactate 1.95w% the rest being rapeseed oil. After a hand mixing at room temperature, the formulation B5 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00241] The results of performance tests are the following:

Blooming: 2.1 % Creaming 0.5% Sedimentation

Viscosity: < 800 cps

Stability: No Syneresis after 8weeks at 40°C

[00242] (Example 13

[00243] Pesticidal compositions in methylated rapeseed oil

[00244] A composition A6 was prepared in methylated Rapeseed oil RADIA 7956 from Oleon and adding Nicosulfuron powder, the nonionic Alkamuls T85V from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture M from example 7 previously heated to 60°C is then introduced to the composition A6 to form the formulation B6. The formulation B6 is as follows: Nicosulfuron (1 OOg/l), Alkamuls T85V 7wt%, C6 Gelator 1.5wt%, n-Propyl L-lactate 4.5w% the rest being methylated rapeseed oil. After a hand mixing at room

temperature, the formulation B6 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.] The results of performance tests are the following:

Blooming: 0.9% creaming 0.4%sedimentation

Viscosity: 300-500 cps

Stability: 7% Syneresis after 8 weeks at 40°C.

Claims

Claims

1. A non-aqueous, emulsifiable formulation comprising

a) at least 3 % by weight of at least one surfactant S which comprises at least two C2-C10 oxyalkylene units and which is free of any aromatic ring, b) at least 10 % by weight of an organic liquid,

c) at least 0.1 % by weight of at least one viscosifier selected from N- hydrocarbyldiamides of general formula (I)

wherein

R^a or R^b is selected from hydrogen or a linear, branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms, with the proviso that either R^a or R^b is hydrogen,

R^c is a cyclic or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 2 to 25 carbon atoms,

with the proviso that said formulation is either free of any surfactant S^* comprising one or more aromatic rings or comprises at least one surfactant S^* comprising one or more aromatic rings in an amount that does not exceed 10 wt.%, based on the total weight of surfactant S and surfactant S^*.

2. The formulation of claim 1 wherein the viscosifier c) is a N- hydrocarbyldiamide composition comprising

c1 ) at least one compound of formula (la)

wherein R¹ is selected from linear or branched or cyclic, saturated or unsaturated, hydrocarbon chains having from 1 to 40 carbon atoms,

R² is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chains having from 1 to 15 carbon atoms, and R³ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms, and

c2) at least one compound of formula (lb)

wherein

R⁴ is selected from linear or branched or cyclic, saturated or unsaturated, hydrocarbon chains having from 1 to 40 carbon atoms,

R⁵ is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chains having from 1 to 15 carbon atoms, and

R⁶ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms.

3. The formulation of claim 1 or 2 wherein the surfactant S is selected from the group consisting of non-ionic surfactants and mixtures of at least one non-ionic surfactant with at least one cationic surfactant.

4. The formulation of any of claims 1 to 3 wherein the surfactant S is selected from non-ionic surfactants.

5. The formulation of any of claims 1 to 4 wherein the surfactant S is selected from polyalkylene glycol esters of fatty acids.

6. The formulation of any of claims 1 to 5 wherein the organic liquid is selected from esterified or non esterified mineral oils, vegetable oils, animal oils or synthetic oils.

7. The formulation of any of claims 1 to 6 wherein components (a) and (b) are present in a weight ratio (a) to (b) ranging from 0.1 to 4, preferably from 0.25 to 1.25.

8. The formulation of any of claims 1 to 7 comprising 10 to 60 wt% of component a) 10 to 90 wt% of component b) and 0.25 to 5 wt% of component c), each wt% value being based on the total weight of the formulation.

9. The formulation of any of claims 1 to 8 comprising as additional component d) at least one biologically active ingredient selected from pharmaceutically active ingredients and agriculturally active ingredients.

10. The formulation of claim 9 wherein the agriculturally active ingredient is selected from herbicides, insecticides, fungicides, parasiticides, plant growth regulators, fertilizers, bactericides and insect repellents.

1 1. The formulation claim 9 or claim 10 which comprises from 1 to 20 wt%, based on the total weight of the formulation, of the biologically active ingredient.

12. Use of the formulation in accordance with any of claims 1 to 8 for

manufacturing pharmaceutical or agricultural compositions.

13. A method for preventing or combatting diseases in animals, such as

mammals, or for preventing or combatting infestation of plants by pests and/or of regulating plant growth comprising the application a mixture obtained by diluting a formulation in accordance with any of claims 9 to 1 1 with water.

14. The method according to claim 13, which is a method for preventing or combatting diseases in animals other than human beings.

15. The method according to claim 13, which is a method for combatting

infestation of plants by pests and/or of regulating plant growth.