FR3117492A1 - Phytosanitary composition comprising, as thickening agent, a polymer in the form of a pulverulent solid - Google Patents

Abstract

Phytosanitary composition (F) comprising at least one phytosanitary active ingredient and as thickening agent a polymer (P) in the form of a pulverulent solid consisting of monomeric units derived from partially or totally salified glutamic acid (GA), and monomeric units of at least one crosslinking agent (RA) carrying at least two glycidyl functions.

Description

Phytosanitary composition comprising, as thickening agent, a polymer in the form of a pulverulent solid

The present invention relates to a phytosanitary composition (F) comprising, as thickening agent, a polymer (P) in the form of a pulverulent solid, the process for preparing said phytosanitary composition (F).

Polymers are widely used today in phytosanitary compositions and represent the second family of products most used in this type of composition. Phytosanitary compositions contain polar phases such as, for example, phases consisting of water, and in most cases require the use of rheology modifying agents, such as, for example, polymers, to increase the viscosity of these polar phases, as well as only to impart a well-defined rheological behavior.

Among the rheology-modifying polymers of the polar phases, we can cite natural polymers, such as for example polysaccharides based on oses or polysaccharides based on derivatives of oses, or else synthetic polymers, of the polyelectrolyte type, anionic or cationic, amphiphilic, linear or branched, cross-linked or non-cross-linked. Predominantly present on the market, synthetic polymers have the property of being deployed in the polar phase, under the effect of electrostatic repulsions due to the presence of charges (negative and/or positive) on the polymeric backbone, linear or branched, uncrosslinked or crosslinked. These rheology modifiers provide both an increase in the viscosity of the polar phase, as well as a certain consistency and/or a stabilizing effect conferred on the phytosanitary composition.

In order to meet the needs of formulators and improve performance, various recent scientific works have reported the development of new, innovative and varied polymer systems. Thus, the polymers used for the purpose of the detergent industries can play a functional role as film-forming agents, rheology modifying agents, allowing the stabilization of the fatty phases in emulsions of the water-in-oil type and of the oil-in-water, stabilization of solid particles (pigments and fillers) or as agents having an impact on the appearance of the formula (transparency, translucency, opacity).

The rheology-modifying polymers of polar phases, and more particularly of aqueous phases, are mainly polyelectrolytes, which result from the radical polymerization of monomers of the (meth)acrylic type, that is to say acrylic acid or methacrylic acid, esters derived from acrylic acid or methacrylic acid, or alternatively acrylamide or methacrylamide derivatives.

Developing new biobased and biodegradable rheology modifiers, as efficient as the synthetic polymers currently used, still constitutes a major challenge to this day. Indeed, until now the solutions mainly used to thicken aqueous phases involve ingredients from petrochemical materials and in particular acrylic acid and its derivatives, methacrylic acid and its derivatives.

Given the growing concern of consumers for a sustainable and responsible economy and development, the substitution of raw materials of petrochemical origin by raw materials of renewable origin to prepare polymers is a priority area of research.

To date, it is described in the literature the use of various natural polymers or coming from renewable raw materials, whose monomeric units come from the family of sugars (glucose, arabinose, xylose, galactose, mannose, ribose, glucuronic acid , etc…) or from the family of amino acids (glutamic acid, aspartic acid, lysine, etc…). These polymers are mostly linear or branched depending on the plant from which they come or according to their manufacturing process.

As an example of a polymer of natural origin, mention may be made of polyglutamic acid (PGA), which is today the subject of numerous research works. It is a predominantly linear polymer and consists of monomeric glutamic acid (GA) units. Glutamic acid is an amino acid characterized by an amine function in the α position and by two carboxylic acid functions (or carboxylates depending on the pH) in the α and γ positions ( cf chemical formula n°1).

Chemical structure of glutamic acid (GA).

One of the ways to increase the branching of a synthetic, natural or of natural origin polymer consists in carrying out crosslinking reactions. The cross-linking of polymer chains aims to connect several polymer chains to each other which, when added to a polar phase, and more particularly to water, appear as a three-dimensional network insoluble in water. water, but swellable with water and then leading to obtaining a chemical gel.

The preparation of crosslinked polymers can be carried out:

• In one step by reacting the monomers and the crosslinking agent during the polymerization reaction, or
• In at least two steps, the first of which consists in preparing the polymer, and the second consists in reacting the polymer with a crosslinking agent to obtain a crosslinked polymer.

There are different crosslinking reactions of polyglutamic acid (PGA), which makes it possible to obtain polymers of natural origin with improved thickening properties in polar media, in particular aqueous media. Among the crosslinking agents known to be used in the crosslinking reaction of (PGA), the polyepoxide derivatives are the most described, because they make it possible to implement crosslinking processes under conditions that respect the environment (moderate temperature, reaction in aqueous media and in the absence of harmful solvents).

However, the implementation of these processes requires diluting the (PGA) at high rates, which leads to the production of an aqueous gel comprising, for 100% of its mass, a mass content less than or equal to 10% of a polymer (P) and difficult to implement by formulators.

From there, a problem which arises is to provide an easy-to-use phytosanitary composition comprising polymers of natural origin and whose raw materials are renewable, and which have thickening properties of polar media and particularly of aqueous media.

A solution of the present invention is a phytosanitary composition (F) comprising at least one active phytosanitary principle and, as thickening agent, a polymer (P) in the form of a pulverulent solid consisting of monomeric units derived from glutamic acid ( GA) partially or completely salified, and monomer units of at least one crosslinking agent (AR) bearing at least two glycidyl functions.

By “powdery solid”, is meant in the sense of the invention a solid consisting of fine particles little or not linked together.

In the polymer (P) present in the phytosanitary composition (F) which is the subject of the present invention, the monomeric units derived from glutamic acid (GA), partially or totally salified, are linked together:

• either in such a way that the amine function of a monomeric unit of glutamic acid (GA) is covalently linked with the carboxylic function located in the alpha (α) position of a second monomeric unit of glutamic acid (GA); the resulting polymer is then called “α-polyglutamic acid” or PAGA ( see chemical formula n°2) partially or totally salified,

Chemical structure of α-polyglutamic acid or PAGA.

either in such a way that the amine function of a monomeric unit of glutamic acid (GA) is covalently linked to the carboxylic function of the side chain located in the gamma (γ) position of a second monomeric unit of glutamic acid (GA); the resulting polymer is then called “γ-polyglutamic acid” or PGGA (cf chemical formula n°3) partially or totally salified.

Chemical structure of γ-polyglutamic acid or PGGA.

In general, the PGA can be prepared chemically according to peptide synthesis methods known to those skilled in the art, in particular passing through stages of selective protection(s), activation, coupling and deprotection(s). The coupling generally consists of a nucleophilic attack of the amine function of a monomeric glutamic acid unit on an activated carboxylic acid function of another monomeric glutamic acid unit.

PGGA can also be obtained by processes comprising at least one microbial fermentation step involving the use of at least one bacterial strain.

Within the meaning of the present invention, in the polymer (P) as defined previously, the term “salified” indicates that the “pendant” carboxylic acid function present on each monomeric unit of glutamic acid (GA) of the polymer (in the gamma position in the case of PAGA or alpha in the case of PGGA) is in an anionic or carboxylate form. The counter-ion of this carboxylate function is a cation derived, for example, from salts of alkali metals such as sodium, potassium or from salts of nitrogenous bases such as amines, lysine or monoethanolamine (HO-CH ₂ - _CH2 - _NH2 ).

By “crosslinking agent (RA) carrying at least two glycidyl functions”, is meant within the meaning of the present invention a crosslinking agent (RA) as defined above whose molecular structure comprises at least two glycidyl units or functions of formula ( I'):

( I')

The cross-linking of the polymer chains of the polymer (P) takes place according to a reaction between the terminal free amine function (-NH2) and/or one or more "pendent" or terminal carboxylic or carboxylate functions (-COOH or -COO ^- ) present in the structure of said polymer (P), and at least one epoxy group present in the structure of the crosslinking agent (AR) bearing at least two glycidyl functions.

By "phytosanitary active ingredient", is meant within the meaning of the present invention means a chemical substance which enters into the composition of a formulation and which demonstrates an effect of protection, care, aid to the growth of plants or to prevent diseases.

The crosslinking agent (RA) may be chosen from the members of the group consisting of:

• Monoethylene Glycol Diglycidyl Ether of formula (I):

(I)

• The compound of formula (II):

(II)

With R representing a hydrogen atom or the glycidyl radical [] , and n representing an integer greater than or equal to 1 and less than or equal to 10;

• The 1,3-propanediol Diglycidyl Ether of formula (III):

(III)

• The 1,2-propanediol Diglycidyl Ether of formula (IV):

(IV)

• 1,4-butanediol Diglycidyl Ether of formula (V):

(V)

• 1,2-butanediol Diglycidyl Ether of formula (VI):

(VI)

• 1,3-butanediol Diglycidyl Ether of formula (VII):

(VII)

• The 1,6-hexanediol Diglycidyl Ether of formula (VIII):

(VIII)

• The compound of formula (IX):

(IX)

With R1 representing a hydrogen atom or the glycidyl radical [ ],

• The compound of formula (X):

(X)

With R1 representing a hydrogen atom or the glycidyl radical [ ],

• The compound of formula (XI):

(XI)

With R1 and R2, independent, representing a hydrogen atom or the glycidyl radical [ ],

• The compound of formula (XII):

(XI)

With m representing an integer greater than or equal to 2,

• The compound of formula (XIII):

(XIII)

With R3 representing a hydrogen atom or the glycidyl radical [ ] and x, y, z, o, p and q, independent of each other, representing an integer greater than or equal to 2 and less than or equal to 10,

Depending on the case, the phytosanitary composition (F) may have one or more of the following characteristics:

• in the polymer (P), for 100% molar of monomeric units derived from glutamic acid (GA), partially or totally salified, the crosslinking agent (RA) represents from 0.5% to 20% molar, more particularly from 0.5% to 15% molar, and even more particularly from 0.5% to 12% molar;
• the polymer (P) further comprises a compound of formula (XIV):

(XIV)

With R4 representing a linear or branched, saturated or unsaturated hydrocarbon radical, optionally comprising at least one functionalized or unfunctionalized hydroxyl function and comprising from 6 to 22 carbon atoms.

• in formula (XIV), R4 represents a hydrocarbon radical chosen from the elements of the group consisting of the radical heptyl, octyl, nonyl, decyl, undecyl, undecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, hydroxyoctadecyl, oleyl, linoleyl, linolenyl, eicosyl and dodecosyl.
• in formula (XIV), R4 represents a hydrocarbon radical chosen from the elements of the group consisting of the n-octyl, n-nonyl, n-decyl, n-undecyl, n-undecenyl, n-dodecyl, n-tetradecyl radical, n-hexadecyl, n-octadecyl, 12-hydroxyoctadecyl, n-eicosyl and n-dodecosyl.
• in said polymer (P), for 100% of the mass of monomeric units derived from glutamic acid (GA), partially or totally salified, the compound of formula (XIV) represents from 1% to 50% by mass.

PGGA can exist in different conformational forms in solution in water. These depend on the inter and intra molecular hydrogen bonds and therefore on the pH, the polymer concentration, the ionic strength of the solution, as well as the temperature. The PGGA chains can thus adopt the form of an α-helix, a β-sheet, aggregates or else be in a disordered and random state.

According to a particular aspect, the polymer (P) is in helical conformation when it is present in a solution at a mass content less than or equal to 0.1% and of which said aqueous solution shows a pH value less than or equal to 7 .

According to a particular aspect, the polymer (P) is in sheet conformation when it is present in an aqueous solution at a mass content less than or equal to 0.1% and of which said aqueous solution shows a pH value greater than 7.

• The phytosanitary composition (F) comprises for 100% of its mass between 0.1% and 10% by mass of said polymer (P), more particularly between 0.1% and 8% by mass, and even more particularly between 0.1% and 5% by mass.
• The phytosanitary active ingredient is a fungicide, bactericide, herbicide, insecticide or plant growth promoting nutrient.

A subject of the present invention is also a process for the preparation of a polymer (P) as defined above, comprising:

A step A) for preparing a Polymer (P) comprising the following sub-steps:

1. A step for preparing a polar phase (PP) comprising partially or totally salified PGA, at least one polar solvent (SP) and at least one crosslinking agent (AR) comprising at least two glycidyl functions,
2. A step of adjusting the pH of the aqueous solution obtained in step a) to a pH of between 3 and 11, and
3. A step of drying by atomization of the polar phase (PP) resulting from step b) so as to obtain the polymer (P) and

A step B) of mixing at least one polymer (P) prepared during step A) with at least one phytosanitary active principle.

Depending on the case, the method according to the invention may have one or more of the following characteristics:

At step a):

• Polyglutamic acid is gamma polyglutamic acid (PGGA),
• All of the monomeric units constituting the PGA are derived from sodium glutamate, potassium glutamate, ammonium glutamate, calcium glutamate, magnesium glutamate or a mixture of these forms,
• The polar phase (PP) comprises for 100% of its mass: from 5% to 80% by mass of the polyglutamic acid (PGA) of the polymer (P), from 0.025% to 8% by mass of the crosslinking agent (RA ), from 12% to 94.975% by weight of at least one polar solvent,
• The polar solvent is chosen from the elements of the group consisting of water, methanol, ethanol, 1-propanol, 2-propanol, isobutanol, tert-butanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, acetone, dimethyl ketone, diethyl ketone, tetrahydropyran, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane and 1,4-dioxane.
• The polar phase (PP) further comprises at least one compound of formula (XIV):

(XIV)

With R4 representing a linear or branched, saturated or unsaturated hydrocarbon radical, optionally comprising at least one hydroxyl function and comprising from 6 to 22 carbon atoms,

R4 representing a hydrocarbon radical chosen from the elements of the group consisting of the radical heptyl, octyl, nonyl, decyl, undecyl, undecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, hydroxyoctadecyl, oleyl, linoleyl, linolenyl, eicosyl and dodecosyl.

According to a particular aspect, in the formula (XIV), R4 represents a hydrocarbon radical chosen from the elements of the group consisting of the radical n-octyl, n-nonyl, n-decyl, n-undecyl, n-undecenyl, n-dodecyl , n-tetradecyl, n-hexadecyl, n-octadecyl, 12-hydroxyoctadecyl, n-eicosyl and n-dodecosyl.

• The content of compound of formula (XIV) in the polar phase (PP) is comprised, for 100% by mass of said polar phase (PP), between 0.05% and 35% by mass, it being understood that the sum of the proportions by mass of the polyglutamic acid (PGA), the crosslinking agent (RA), the polar solvent (SP) and the compound of formula (XIV) is equal to 100%.

At step b):

• The pH is between 4 and 10, preferably between 5 and 7,

At step c):

• Drying is carried out using an atomizer implementing an air flow and a nozzle,
• The inlet temperature of the air flow is between 80 and 180°C, preferably between 100 and 170°C.

According to a particular aspect, the polar phase (PP) comprises for 100% of its mass: from 5% to 70% by mass of the polyglutamic acid (PGA) of the polymer (P), from 0.025% to 7% by mass of the crosslinking agent (RA), from 23% to 94.975% by mass of at least one polar solvent (SP).

According to an even more particular aspect, the polar phase (PP) comprises for 100% of its mass: from 5% to 60% by mass of polyglutamic acid (PGA) of the polymer (P), from 0.025% to 6% by mass of the crosslinking agent (RA), from 34% to 94.975% by weight of at least one polar solvent (SP).

According to another particular aspect, the polar solvent (SP) is chosen from the following list: water, ethanol, acetone, dimethyl ketone.

According to another even more particular aspect, the polar solvent (SP) is water.

According to another particular aspect, R4 representing a hydrocarbon radical is chosen from the elements of the group consisting of the n-octyl, n-nonyl, n-decyl, n-undecyl, n-undecenyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 12-hydroxy octadecyl, n-eicosyl and n-dodecosyl.

According to another particular aspect, the content of compound of formula (XIV) in the polar phase (PP) is comprised, for 100% by mass of said polar phase (PP), between 0.05% and 20% by mass, and even more particularly between 0.05% and 15% by mass, it being understood that the sum of the proportions by mass of the polyglutamic acid (PGA), of the crosslinking agent (RA), of the polar solvent (SP) and of the compound of formula ( XIV) is equal to 100%.

The present invention also relates to:

• the use of the polymer (P) as defined above, as a thickening and/or emulsifying and/or stabilizing agent for an aqueous liquid phytosanitary composition for fungicidal, bactericidal or insecticide use;
• the use of said liquid aqueous phytosanitary composition (F) as defined previously, for preventing and/or treating plants liable to be affected or affected by a fungal disease and/or by parasitic plants and/or by a bacterial disease and/or by insects; And
• a process for treating a plant, characterized in that it comprises at least one step of applying the phytosanitary composition (F) as defined previously to the plant by sprinkling and/or by spraying and/or by watering and/ or in any other form allowing said application.

According to a particular aspect, said use consists in thickening polar phases such as for example aqueous, alcoholic or aqueous-alcoholic phases or polar phases comprising polyols such as glycerol.

According to another particular aspect, said use consists in stabilizing an emulsion of the oil-in-water type, or of the water-in-oil type, by conferring a homogeneous appearance on said emulsion during storage under different conditions, and more particularly at 25 °C for a period at least equal to one month, and more particularly at 4°C for a period at least equal to one month, and more particularly at 45°C for a period at least equal to one month.

According to another particular aspect, said use consists in stabilizing solid particles in phytosanitary compositions (F).

These solid particles to be suspended can take on different geometries, regular or irregular, and take the form of beads, balls, rods, flakes, lamellae or polyhedrons. These solid particles are characterized by an average apparent diameter of between one micrometer and five millimeters, more particularly between ten micrometers and one millimeter.

Among the solid particles which can be suspended and stabilized by the polymer (P) as defined above in phytosanitary compositions, there are micas, iron oxide, titanium oxide, zinc oxide , aluminum oxide, talc, silica, kaolin, clays, boron nitride, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, inorganic color pigments, polyamides such as nylon-6, polyethylenes, polypropylenes, polystyrenes, polyesters, acrylic or methacrylic polymers such as polymethylmethacrylates, polytetrafluoroethylene, crystalline or microcrystalline waxes, porous spheres, selenium sulphide, zinc pyrithione, starches , alginates, plant fibers, Loofah particles, sponge particles.

Said phytosanitary composition (F), object of the present invention, is in particular in the form of an aqueous solution, an emulsion or a microemulsion with an aqueous continuous phase, an emulsion or a microemulsion with a continuous phase oily, an aqueous gel, a foam, or even in the form of an aerosol. It can be applied directly to the surface of the skin or via any type of support intended to be brought into contact with the surface of the skin (paper, wipe, textile).

In general, said phytosanitary composition (F) which is the subject of the present invention, also comprises at least one or more auxiliary compounds chosen from fatty phases, foaming and/or detergent surfactants, thickening and/or gelling surfactants, thickeners and/or gelling agents, stabilizing agents, film-forming compounds, solvents and co-solvents, hydrotropic agents, plasticizing agents, opacifying agents, pearlescent agents, superfatting agents, sequestering agents, chelating agents, antioxidants, fragrances, essential oils, preservatives, conditioning agents.

In general, the phytosanitary (F) according to the invention may comprise excipients and/or active principles usually used in the field of formulations, in particular phytosanitary.

Among the fatty phases present in the phytosanitary composition (F) according to the invention, mention may be made of oils and waxes.

By oil is meant a compound and/or a mixture of compounds insoluble in water, and liquid at 25°C, and more particularly:

- Linear alkanes comprising from eleven to nineteen carbon atoms;

- Branched alkanes, comprising seven to forty carbon atoms, such as isododecane, isopentadecane, isohexadecane, isoheptadecane, isooctadecane, isononadecane or isoeicosane), or mixtures of certain between them such as those mentioned below and identified by their INCI name: C _7-8 isoparaffin, C _8-9 isoparaffin, C _9-11 isoparaffin, C _9-12 isoparaffin, C _9-13 isoparaffin, C _9-14 isoparaffin, C _9-16 isoparaffin, C _10-11 isoparaffin, C _10-12 isoparaffin, C _10-13 isoparaffin, C _11-12 isoparaffin, C _11-13 isoparaffin, C _11-14 isoparaffin, C _12-14 isoparaffin, C _12-20 isoparaffin, C _13-14 isoparaffin, C _13-16 isoparaffin;

- Cyclo-alkanes optionally substituted by one or more linear or branched alkyl radicals;

- White mineral oils, such as those marketed under the following names: Marcol™52, Marcol™82, Drakeol™6VR, Eolane™130, Eolane™150;

- Hemisqualane (or 2,6,10-trimethyl-dodecane; CAS number: 3891-98-3), squalane (or 2,6,10,15,19,23-hexamethyltetracosane), hydrogenated polyisobutene or hydrogenated polydecene;

- Mixtures of alkanes comprising from 15 to 19 carbon atoms, said alkanes being linear alkanes, branched alkanes and cyclo-alkanes, and more particularly the mixture (M ₁ ) which comprises for 100% of its mass, a mass proportion of branched alkanes greater than or equal to 90% and less than or equal to 100%; a mass proportion of linear alkanes greater than or equal to 0% and less than or equal to 9%, and more particularly less than 5% and a mass proportion of cycloalkanes greater than or equal to 0% and less than or equal to 1%, for for example the mixtures marketed under the names Emogreen™L15 or Emogreen™L19;

- Fatty alcohol ethers of formula (II'):

Z ₁ -OZ ₂ (II'),

in which Z ₁ and Z ₂ , which are identical or different, represent a linear or branched alkyl radical containing from five to eighteen carbon atoms, for example dioctyl ether, didecyl ether, didodecyl ether, dodecyl octyl ether, dihexadecyl ether, (1 ,3-dimethyl butyl) tetradecyl ether, (1,3-dimethyl butyl) hexadecyl ether, bis(1,3-dimethyl butyl) ether or dihexyl ether.

- Mono-esters of fatty acids and alcohols of formula (III’):

R' ₁ -(C=O)-O-R' ₂ (III'),

in which R' ₁ -(C=O) represents an acyl radical, saturated or unsaturated, linear or branched, containing from eight to twenty-four carbon atoms, and R'2 represents, independently of R' ₁ , a hydrocarbon chain saturated or unsaturated, linear or branched containing from one to twenty-four carbon atoms, for example methyl laurate, ethyl laurate, propyl laurate, isopropyl laurate, butyl laurate, 2-butyl laurate, laurate hexyl cocoate, methyl cocoate, ethyl cocoate, propyl cocoate, isopropyl cocoate, butyl cocoate, 2-butyl cocoate, hexyl cocoate, methyl myristate, ethyl myristate, propyl myristate, isopropyl myristate, butyl myristate, 2-butyl myristate, hexyl myristate, octyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, isopropyl, butyl palmitate, 2-butyl palmitate, hexyl palmitate, octyl palmitate, oleate methyl, ethyl oleate, propyl oleate, isopropyl oleate, butyl oleate, 2-butyl oleate, hexyl oleate, octyl oleate, methyl stearate, ethyl stearate, propyl stearate, isopropyl stearate, butyl stearate, 2-butyl stearate, hexyl stearate, octyl stearate, isostearate of methyl, ethyl isostearate, propyl isostearate, isopropyl isostearate, butyl isostearate, 2-butyl isostearate, hexyl isostearate, isostearyl isostearate;

- Di-esters of fatty acids and glycerol of formula (IV') and of formula (V'):

R' ₃ -(C=O)-O-CH ₂ -CH(OH)-CH ₂ -O-(C=O)-R' ₄ (IV')

R' ₅ -(C=O)-O-CH ₂ -CH[O-(C=O)-R' ₆ ]-CH ₂ -OH (V'),

formulas (IV') (V') in which R' ₃ -(C=O), R' ₄ -(C=O), R' ₅ -(C=O), R' ₆ -(C=O) , which are identical or different, represent an acyl group, saturated or unsaturated, linear or branched, comprising from eight to twenty-four carbon atoms;

- Tri-esters of fatty acids and glycerol of formula (VI'):

R' ₇ -(C=O)-O-CH ₂ -CH[O-(C=O)-R'' ₈ ]-CH ₂ -O-(C=O)-R'' ₉ (VI') ,

in which R' ₇ -(C=O), R' ₈ -(C=O) and R' ₉ -(C=O), identical or different, represent an acyl group, saturated or unsaturated, linear or branched, comprising eight to twenty-four carbon atoms.

- Vegetable oils, such as phytosqualane, sweet almond oil, coconut oil, castor oil, jojoba oil, olive oil, rapeseed oil, l peanut oil, sunflower oil, wheat germ oil, corn germ oil, soybean oil, cottonseed oil, alfalfa oil, poppy seed oil, pumpkin oil, evening primrose oil, millet oil, barley oil, rye oil, safflower oil, bancoulier oil, passionflower, hazelnut oil, palm oil, shea butter, apricot kernel oil, calophyllum oil, sysymbrium oil, avocado oil, calendula, oils from flowers or vegetables;

- Ethoxylated vegetable oils.

Preferably, the composition according to the invention comprises at least one oil chosen from the elements of the group consisting of castor oil, paraffin oils, cocoyl caprylate/caprate, isopropyl myristate, capric caprylic triglyceride.

Among the fatty phases that can be associated with the phytosanitary composition (F) according to the invention, mention may be made of waxes. The latter are more particularly chosen from beeswax, carnauba wax, candelilla wax, ouricoury wax, Japan wax, cork fiber wax, sugar cane wax, waxes paraffins, lignite waxes, microcrystalline waxes, lanolin wax; ozokerite; polyethylene wax; silicone waxes; vegetable waxes; fatty alcohols and fatty acids which are solid at room temperature; solid glycerides at room temperature.

As regards the auxiliary compounds, among the foaming and/or detergent anionic surfactants which can be combined with the phytosanitary composition (F) according to the invention, mention may be made of alkali metal salts, alkaline-earth metal salts, ammonium salts, amine salts, amino alcohol salts of alkyl ether sulphates, alkyl sulphates, alkylamidoether sulphates, alkylarylpolyether sulphates, monoglyceride sulphates, alpha-olefin sulphonates, paraffin sulphonates , alkyl phosphates, alkyl ether phosphates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, alkyl carboxylates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfo- acetates, alkyl sarcosinates, acylisethionates, N-acyl taurates, acyl lactylates, N-acyl derivatives of amino acids, N-acyl derivatives of peptides, N-acyl derivatives of proteins, fatty acids .

Among the foaming and/or detergent amphoteric surfactants optionally present in the phytosanitary composition (F) according to the invention, mention may be made of alkylbetaines, alkylamidobetaines, sultaines, alkylamidoalkylsulfobetaines, imidazoline derivatives, phosphobetaines, amphopolyacetates and amphopropionates.

Among the foaming and/or detergent cationic surfactants optionally present in the phytosanitary composition (F) according to the invention, mention may be made in particular of quaternary ammonium derivatives.

Among the foaming nonionic surfactants and/or detergents optionally present in composition (F) according to the invention, mention may be made more particularly of alkylpolyglycosides comprising an aliphatic radical, linear or branched, saturated or unsaturated, and comprising from 8 to 12 carbon atoms. of carbon ; castor oil derivatives, polysorbates, coconut amides, N-alkylamines.

As examples of thickening and/or gelling surfactants optionally present in the phytosanitary composition (F) according to the invention, mention may be made of:

- optionally alkoxylated alkylpolyglycoside fatty esters, and more particularly ethoxylated methylpolyglucoside esters such as PEG 120 methyl glucose trioleate and PEG 120 methyl glucose dioleate marketed respectively under the names GLUCAMATE™ LT and GLUMATE™ DOE120;

- alkoxylated fatty esters such as PEG 150 pentaerythrytyl tetrastearate marketed under the name CROTHIX™ DS53, PEG 55 propylene glycol oleate marketed under the name ANTIL™ 141;

- polyalkylene glycol carbamates with fatty chains such as PPG 14 laureth isophoryl dicarbamate sold under the name ELFACOS™ T211, PPG 14 palmeth 60 hexyl dicarbamate sold under the name ELFACOS™ GT2125 .

As examples of emulsifying surfactants optionally present in the phytosanitary composition (F) according to the invention, mention may be made of nonionic surfactants, anionic surfactants, cationic surfactants.

As examples of emulsifying nonionic surfactants optionally present in the phytosanitary composition (F) according to the invention, ethoxylated castor oil and ethoxylated hydrogenated castor oil, for example the product marketed under the name SIMULSOL™ 989; compositions comprising glycerol stearate and poly(ethoxylated) stearic acid with between 5 moles and 150 moles of ethylene oxide, for example the composition comprising stearic acid (ethoxylated) with 135 moles of ethylene and glycerol stearate marketed under the name SIMULSOL™ 165; ethoxylated sorbitan esters, for example the products marketed under the name MONTANOX™; ethoxylated mannitan esters; sucrose esters; methylglucoside esters.

As examples of emulsifying anionic surfactants optionally present in the phytosanitary composition (F) according to the invention, mention may be made of decyl phosphate, cetyl phosphate marketed under the name AMPHISOL™, glyceryl stearate citrate; cetearyl sulfate; the composition arachidyl/behenyl phosphates and arachidyl/behenyl alcohols marketed under the name SENSANOV™WR; soaps, for example sodium stearate or triethanolammonium stearate, N-acylated derivatives of salified amino acids such as, for example, stearoyl glutamate.

As examples of emulsifying cationic surfactants optionally present in the phytosanitary composition (F) according to the invention, mention may be made of amine oxides, quaternium-82, cetyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, cetyl pyridinium chloride, benzalkonium chloride, benzethonium chloride, and the surfactants described in document WO96/00719 and mainly those whose fatty chain comprises at least 16 carbon atoms.

As examples of opacifying and/or pearlescent agents optionally present in the phytosanitary composition (F) according to the invention, mention may be made of sodium palmitate, sodium stearate, sodium hydroxystearate, magnesium palmitate, stearate magnesium, magnesium hydroxystearate, ethylene glycol monostearate, ethylene glycol distearate, polyethylene glycol monostearate, polyethylene glycol distearate, fatty alcohols containing 12 to 22 carbon atoms.

As examples of solvents and co-solvents optionally present in the phytosanitary composition (F) according to the invention, mention may be made of water, organic solvents, for example glycerol, diglycerol, glycerol oligomers, ethylene glycol , propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, xylitol, erythritol, sorbitol, water-soluble alcohols such as ethanol, isopropanol or butanol, mixtures of water and of said organic solvents, propylene carbonate, ethyl acetate, benzyl alcohol, dimethyl sulfoxide (DMSO).

As examples of thickening and/or gelling agents optionally present in the phytosanitary composition (F) according to the invention, mention may be made of polysaccharides consisting solely of oses, such as glucans or glucose homopolymers, glucomannoglucans, xyloglycans, galactomannans whose degree of substitution (DS) of the D-galactose units on the D-mannose main chain is between 0 and 1, and more particularly between 1 and 0.25, such as the galactomannans from cassia gum ( DS = 1/5), locust bean gum (DS = 1/4), tara gum (DS = 1/3), guar gum (DS = 1/2), fenugreek (SD = 1).

As examples of thickening and/or gelling agents optionally present in the phytosanitary composition (F) according to the invention, mention may be made of polysaccharides consisting of derivatives of oses, such as sulphated galactans and more particularly carrageenans and agar, uronans and more particularly algins, alginates and pectins, heteropolymers of oses and uronic acids and more particularly xanthan gum, gellan gum, gum arabic and karaya gum exudates, glucosaminoglycans.

As examples of thickening and/or gelling agents optionally present in the phytosanitary composition (F) according to the invention, mention may be made of cellulose, cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose , silicates, starch, hydrophilic derivatives of starch, polyurethanes.

As examples of stabilizing agents optionally present in the phytosanitary composition (F) according to the invention, mention may be made of microcrystalline waxes, and more particularly ozokerite, mineral salts such as sodium chloride or magnesium chloride.

As examples of antisectide agents which can be combined with the phytosanitary composition (F) according to the invention, mention may be made of trichlorfone, triflumerone, fenthion, bendiocarb, cyromazine, dislubenzurone, dicyclanil, fluazurone , amitraz, deltamethrin, cypermethrin, chlorfenbinphose, flumethrin, ivermectin, abermectin, avermectin, doramectin, moxidectin, zeti-cypermethrin, diazinone, spinosad, imidacloprid, nitenpyran, pyriproxysene, sipronil, cythioate, lufenurone, selamectin, milbemycin oxime, chlorpyrifose, coumaphose, propetamphose, alpha-cypermethrin, highciscypermethrin, ivermectin, diflubenzurone, cyclodiene, carbamate and benzoyl urea.

As examples of antimicrobial agents which can be combined with the phytosanitary composition (F) according to the invention, mention may be made of sulfonamides, aminoglycosides such as, for example, neomycin, tobramycin, gentamycin, amikacin, kanamycin, spectinomycin, paromomycin, netilmicin, polypeptides, cephalosporins, oxazolidinones such as for example ciprofloxacin, levofloxacin, ofloxacin.

Examples:

The following examples illustrate the invention without however limiting it.

Example 1: Preparation of a sodium PGGA according to the invention crosslinked with Polyethylene glycol Diglycidyl Ether and atomized:

The synthesis process comprises the following 4 steps:

Step 1): Production of an aqueous gel of sodium PGGA:

200 grams of demineralized water are stirred with a Rayneri ^™ brand mechanical stirrer equipped with a deflocculating-type rotor and 20 grams of PGGA, marketed by the Lubon Company under the name “cosmetic grade PGGA”, are then slowly added into the vortex,

Step 2): pH adjustment:

The pH of the mixture from step 1) is adjusted to a value between 5.5 and 6.0 using an aqueous solution of 5 M HCl (temperature = 20°C),

Step 3): Adding the crosslinker:

In the mixture of step 2), are added 1.2 grams of Polyethylene glycol Diglycidyl Ether (PEGDGE) of average molecular weight of the order of 500 g/mol,

Step 4): Atomization:

The aqueous solution obtained in step 3) is concentrated by passage through an atomizer whose operating parameters are as follows:

• Solution introduction rate = 4 ml/min,
• Spray nozzle pressure = 1.5 bars,

• Circulating air temperature = 150°C,

Composition (E1) is finally isolated in the form of a pulverulent powder.

Example 2: Preparation of a sodium PGGA according to the invention crosslinked with 1,4-Butanediol diglycidyl ether and atomized:

The synthesis process of Example 1 is reproduced by replacing the 1.2 grams of Polyethylene glycol Diglycidyl Ether (PEGDGE) with 0.48 grams of 1,4-Butanediol Diglycidyl Ether marketed under the name ERISYS ^TM GE 21 with EMERALD Company.

The composition (E2) obtained is finally isolated in the form of a pulverulent powder.

Evaluation of the crosslinked and atomized sodium PGGAs obtained in the two preceding examples:

The evaluation of compositions (E1) and (E2) (crosslinked and atomized sodium PGGAs), obtained in the two previous examples, was carried out as follows:

• In a 400 ml tall beaker, dispersion of 4 grams of the polymer compositions to be tested in pulverulent powder form in 196 grams of water with stirring using a Rayneri ^™ brand mechanical stirrer equipped with a deflocculating type until a homogeneous gel is obtained,

• Measurement of the dynamic viscosity using a Brookfield viscometer and type RVT Speed 5 by choosing the appropriate spindle,

• Addition of 0.1% of NaCl to the gel previously produced and stirring with a Rayneri ^™ brand mechanical stirrer equipped with a deflocculator-type rotor until the mixture is homogenized,

• Measurement of the dynamic viscosity using the same viscometer as before, always choosing the appropriate spindle.

A control was produced from non-crosslinked PGGA marketed by the Lubon Company under the name “cosmetic grade PGGA”.

The measured dynamic viscosity values are collated in the table below:

Composition Nature Crosslinking Viscosity in mPa.s of the 2% polymer gel Viscosity in mPa.s of the 2% polymer + 0.1% NaCl gel Witness ^a) No 176 (mobile 2) 128 (mobile 2) Membership (E1) PEGDGE 30,400 (mobile 5) 9320 (phone 3) Membership (E2) ERISYS ^TM GE 21 41,520 (mobile 5) /

1. Non-crosslinked PGGA marketed by the Lubon Company under the name “cosmetic grade PGGA”,

Table 1: Dynamic viscosities of aqueous gels obtained with compositions (E1) and (E2).

The control sodium PGGA gels (non-crosslinked and non-atomized) exhibit viscosities of between 100 and 200 mPa.s in the presence or absence of NaCl.

In the absence of NaCl, crosslinked and atomized sodium PGGA gels have viscosities respectively equal to 30400 mPa.s in the case where the crosslinker is PEGDGE and 41520 mPa.s with ERISYS ^TM GE 21 as crosslinker .

In the presence of NaCl, the viscosity of the gel of sodium PGGA crosslinked by PEGDGE and atomized is equal to 9320 mPa.s.

The compositions (E1) and (E2) according to the invention therefore make it possible to thicken aqueous phases.

Claims (21)

Phytosanitary composition (F) comprising at least one phytosanitary active ingredient and as thickening agent a polymer (P) in the form of a pulverulent solid consisting of monomeric units derived from partially or totally salified glutamic acid (GA), and monomeric units of at least one crosslinking agent (RA) carrying at least two glycidyl functions. Phytosanitary composition (F) according to Claim 1, characterized in that in the polymer (P), the crosslinking agent (AR) is chosen from the members of the group consisting of:

• Ethylene Glycol Di Glycidyl Ether of Formula (I)

(I)

• the compound of formula (II)

(II)
With R representing the hydrogen atom or the glycidyl radical [], and n which represents an integer greater than or equal to one and less than or equal to 10;

• The 1,3 propanediol DiGlycidyl ether of formula (III)

(III)

• The 1,2 propanediol DiGlycidyl ether of formula (IV)

(IV)

• The 1,4 butanediol Di Glycidyl ether of formula (V)

(V)
- 1,2 butanediol Di Glycidyl ether of formula (VI)
(VI)

• The 1,3 butanediol Di Glycidyl ether of formula (VII)

(VII)

• The 1,6 hexanediol DI Glycidyl ether of formula (VIII)

(VIII)

• The compound of formula (IX)

(IX)
With R1 representing the hydrogen atom or the glycidyl radical [];

• The compound of formula (X)

(X)
With R1 and R2, independent, which represent the hydrogen atom or the glycidy radical []

• The compound of formula (XI)

(XI)
With m representing an integer greater than or equal to 2

• The compound of formula (XII)

(XI)
With R3 representing the hydrogen atom or the glycidyl radical [], and x, y, z, o, p and q, independent of each other, represent an integer greater than or equal to 2 and less than or equal to 10. Phytosanitary composition (F) as defined in one of Claims 1 or 2, characterized in that in the polymer (P), for 100% molar of monomeric units derived from glutamic acid (GA), partially or totally salified, the crosslinking agent (RA) represents from 0.5% to 20% molar. Phytosanitary composition (F) according to any one of Claims 1 to 3, characterized in that the said polymer (P) additionally comprises a compound of formula (XIV):
(XIV)
With R4 which represents a linear or branched, saturated or unsaturated hydrocarbon radical, containing from 6 to 22 carbon atoms Phytosanitary composition (F) according to Claim 4, characterized in that in formula (XIV), R4 represents a hydrocarbon radical chosen from the elements of the group consisting of the octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oleyl, linoleyl, linolenyl, eicosyl, dodecosyl. Phytosanitary composition (F) according to any one of Claims 4 or 5, characterized in that in the polymer (P), for 100% of the mass of monomeric units derived from glutamic acid (GA), partially or totally salified, the compound of formula (XIV) represents from 1% to 50% by mass. Phytosanitary composition (F) according to one of Claims 1 to 6, characterized in that it comprises, for 100% of its mass, between 0.1% and 10% by mass of the said polymer (P). Phytosanitary composition (F) according to one of Claims 1 to 7, characterized in that the phytosanitary active principle is a fungicide, a bactericide, a herbicide, an insecticide or a nutritive element which promotes the growth of plants. Process for the preparation of a phytosanitary composition (F) as defined in one of Claims 1 to 8, comprising:
a step (A) for preparing a Polymer (P) comprising the following sub-steps:

1. A step for preparing a polar phase (PP) comprising polyglutamic acid, partially or totally salified, at least one polar solvent (SP) and at least one crosslinking agent (AR) comprising at least two glycidyl functions,
2. A step of adjusting the pH of the aqueous solution obtained in step a) to a pH of between 3 and 11,
3. A step of drying by atomization of the polar phase (PP) resulting from step b) so as to obtain the polymer (P),

A step B) of mixing at least one polymer (P) prepared during step A) with at least one phytosanitary active principle. Process according to Claim 9, characterized in that in stage a) the polyglutamic acid is gamma-polyglutamic acid (PGGA). Process according to Claim 10, characterized in that in step a) all of the monomeric units constituting the polyglutamic acid (PGA) are derived from sodium glutamate, potassium glutamate, ammonium glutamate, glutamate calcium, magnesium glutamate or a mixture of these forms. Process according to one of Claims 9 to 11, characterized in that in stage a) the polar phase (PP) comprises for 100% of its mass:

• From 5% to 80% by weight of the polymer (P) as defined in one of claims 1 to 8,
• From 0.025% to 8% by weight of at least one crosslinking agent (RA) as defined in claim 2,
• From 12% to 94.975% by weight of at least one polar solvent (SP).

Process according to one of Claims 9 to 12, characterized in that in step a) the polar solvent (SP) is chosen from the elements of the group consisting of water, methanol, ethanol, 1 -propanol, 2-propanol, iso-butanol, tert-butanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, acetone, dimethyl ketone, diethyl ketone, tetrahydropyran, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane. Process according to one of Claims 9 to 13, characterized in that in stage a) the polar phase also comprises at least one compound of formula (XIV):
(XIV)
With R4 which represents a linear or branched, saturated or unsaturated hydrocarbon radical, optionally comprising at least one hydroxyl function and comprising from six to 22 carbon atoms Process according to Claim 14, characterized in that R4 represents a hydrocarbon radical chosen from the elements of the group consisting of the radical octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oleyl, linoleyl , linolenyl, eicosyl, dodecosyl. Process according to Claim 14 or 15, characterized in that the content of compound of formula (XIV) in the polar phase (PP) is comprised, for 100% by mass of the said polar phase (PP), between 0.05% and 35 % by mass, it being understood that the sum of the proportions by mass of the polyglutamic acid, of the crosslinking agent (RA), of the polar solvent (SP) and of the compound of formula (XIV) is equal to 100% Method according to one of Claims 9 to 16, characterized in that step c) is carried out using an atomizer implementing an air flow and a nozzle. Process according to Claim 17, characterized in that the inlet temperature of the air flow is between 80°C and 180°C, preferably between 100°C and 170°C. Use of said polymer (P) as defined in one of Claims 1 to 9, as a thickening and/or emulsifying and/or stabilizing agent for a phytosanitary composition for fungicidal, bactericidal or insecticide use. Use of said phytosanitary liquid composition (F) as defined in one of claims 1 to 9 for preventing and/or treating plants liable to be affected or affected by a fungal disease and/or by parasitic plants and/or by bacterial disease and/or insects. Process for treating a plant, characterized in that it comprises at least one step of applying the phytosanitary composition (F), as defined in one of Claims 1 to 9, by sprinkling and/or by spraying and / or by spraying and/or in any other form allowing said application.