WO2006100259A1

WO2006100259A1 - Method of treating plants using an aqueous silicon dispersion containing a plant protection additive

Info

Publication number: WO2006100259A1
Application number: PCT/EP2006/060944
Authority: WO
Inventors: Michel Feder; Alexandre Busuttil; Paul Branlard
Original assignee: Rhodia Chimie
Priority date: 2005-03-23
Filing date: 2006-03-22
Publication date: 2006-09-28
Also published as: FR2883452A1

Abstract

The invention relates to a plant treatment and/or protection method. More specifically, the invention relates to a surface treatment method which is used to look after a plant (tree) in a simple, cost-effective manner. The inventive method essentially consists in applying at least one dressing to the plant, said dressing being obtained from a preferably-polymer composition that can be hardened into a preventive and/or curative synthetic coating by means of drying, chemical crosslinking or drying and chemical crosslinking, particularly at ambient temperature. For example, the composition comprises an aqueous silicon dispersion that can be hardened by means of drying and by condensation crosslinking. The dressing is obtained prior to the application on the plant or directly during said application, for example by means of spatula coating. The dressing is self-adhesive and elastic. The invention also relates to the composition (e.g. aqueous silicon) having one ore more added plant protection active principles.

Description

PROCESS FOR TREATING PLANTS USING AQUEOUS SILICONE DISPERSION CONTAINING PHYTOSANITARY ADDITIVE

The field of the invention is that of plant treatment methods and means useful for this purpose.

The phytosanitary treatments concerned are, in particular, preventive and / or curative protective treatments, disease control, cicatrization or even aid for the growth of plants (e.g. plants, trees-especially fruit-).

The problem underlying the invention is the development of new methods of treatment and protection of plants such as plants - especially ornamental plants - or trees - especially fruit trees.

In the same way as individuals in the animal kingdom, plants are subject to diseases, more or less superficial wounds and / or mutilations, or even problems of local decay. Specifically, the phytosanitary needs of plants can be:

• physical protection when the bark is torn off, • help to heal wounds or cut branches,

• clogging of cankers (common especially on apple trees),

• the clogging of cavities colonized by insects or other parasites (larvae) ...,

• and / or the filling of hollow parts (forks, branch departure) likely to accumulate stagnant water, which favors decay.

As regards the animal kingdom, it is known to remedy comparable problems using, for example, bandages, bandages or compresses soaked or not with active products.

It is known to use silicones as a support in dressings or other means of treating superficial wounds occurring in individuals of the animal kingdom, in particular in humans. Thus, patent application WO-A-01/64258 describes the use in a dressing of silicone foam intended to support a natural polymer such as collagen. The patent application WO-A-00/53139 describes a dressing comprising an adhesive tape and a silicone elastomer pad fixed on the adhesive side of the band of the same name and intended to be applied to the wound. The transposition of these means of treatment to the plant kingdom is not at all common and, in any case, there is no practical way to treat and protect plants, as can be done with for example, using animal dressings.

There are good on the market healing sealants for plants, but these pasty products are based on tars (eg pine tar) or mixtures of vegetable oils / resins and suffer from many drawbacks: they are non-curable, difficult to apply, toxic even flammable, among others.

Thus, one of the essential objectives of the present invention is to fill this gap by proposing a technique and means of treatment and / or protection of plants, which do not have the aforementioned drawbacks. Another essential objective of the invention is to provide a technique and means of treatment and / or protection of plants, which are simple to implement (application on the plant).

Another essential objective of the invention is to provide a technique and means for treating and / or protecting plants, which require only one intervention for the application, to the exclusion of any other intervention for the withdrawal. means implemented.

Another essential objective of the invention is to provide a technique and means for treating and / or protecting plants, which are non-toxic (e.g., without volatile solvent).

Another essential objective of the invention is to provide a technique and means for treating and / or protecting plants, which are not dangerous (e.g., non-flammable).

Another essential objective of the invention is to provide a technique and means of treatment and / or protection of plants, which are odorless. Another essential objective of the invention is to provide a technique and means of treatment and / or protection of plants, which are environmentally friendly. Another essential objective of the invention is to provide a technique and means for treating and / or protecting plants, which make it possible to form on the plants to be treated an effective protective barrier, and which is preferably elastic for marry the shape of plant supports and adapt well to dimensional variations. Another essential objective of the invention is to provide a method and means for treating and / or protecting plants which make it possible to fix on the plants supports of active phytosanitary principles, so as to optimize the preventive and curative effects of these plants. phytosanitary active principles, or even prolong them for long periods. Another essential objective of the invention is to provide a method and means for treating plants which is simple and economical to implement. Another essential object of the invention is to provide a method and means for treating plants which overcome the difficulty of adhering a dressing to a plant support.

Another essential objective of the invention is to propose a method and means:

• for the protection of plants whose bark is torn off

• and / or for the healing of wounds and cut branches on plants

• and / or for clogging: → cankers, especially on fruit trees

→ and / or cavities colonized by plant pests → and / or hollow parts of plants particularly prone to the accumulation of stagnant water and thus rotting.

These objectives, among others, are achieved by the present invention, which first of all relates to a method for treating and / or protecting a plant, characterized in that it consists essentially of applying to the plant at least one dressing. obtained from a composition-preferably polymer-hardenable either under the effect of drying, or by chemical crosslinking, or by drying and chemical crosslinking, particularly at room temperature, preventive and / or curative synthetic coating.

The expression "chemical crosslinking" is intended to denote all the bridging reactions between the macromolecular chains by addition, polyaddition, condensation, polycondensation, dehydrogenopolycondensation, of a conventional and / or ionic and / or radical nature, this crosslinking possibly being triggered. and / or accelerated under the action of heat, radiation, electron beam and / or using a catalyst.

Without this being limiting, the curable-preferably polymer-curable composition used in the process according to the invention is advantageously a putty, that is to say a viscous composition based on a polymer material intended to make liquid coatings, especially sealing, filling, fixing.

All the merit of the inventors is to have had the idea to implement a fluid formulation, harmless, environmentally neutral and easy to apply on plants, hardenable fairly quickly in ambient conditions, to form a dressing-advantageously elastic and self-adherent-. In addition, this dressing may carry phytosanitary active principles, able to diffuse more or less slowly to the plant and to allow preventive and / or curative treatment (healing / pesticidal effect) and / or the protection and / or development (growth accelerator) of plants such as plants and fruit trees.

By way of illustration, it can be pointed out that the curable-preferably polymer-curable composition used in the process according to the invention is chosen, for example, from polyurethane mastics, silicone mastics or MSP ("Modified Silicon Polymer") type mastics. eg: polyoxyalkylene (propylene) silylated), acrylic mastics and mixtures thereof.

According to a preferred embodiment (MP) of the invention, the curable composition comprises at least one aqueous dispersion - preferably polymer - hardenable by removal of water.

The aqueous homologues (emulsions) of the mastics listed above are examples of useful aqueous dispersions.

According to an even more preferred embodiment (MP *) of the invention, the method for treating and / or protecting a plant consists essentially of applying to the plant at least one dressing obtained from a silicone composition which is extensible. , curable and comprising at least one aqueous dispersion of silicone oil (s) comprising: -A- 100 parts by weight of at least one polyorganosiloxane oil (A) capable of crosslinking by condensation, if necessary in the presence of an agent of crosslinking (B), an elastomer; If necessary, from 0.1 to 10 parts by weight of at least one crosslinking agent

(B); -C optionally, up to 10 parts by weight of at least one adhesion promoter (C) - preferably a silane-;

Optionally, up to 200 parts by dry weight of a filler (D); Optionally, a catalytically effective amount of at least one catalytic curing compound (E) of up to 3 parts by weight; At least one emulsifier (F);

-G- optionally at least one functional additive (G) for treatment and / or protection of the plant; -H- and water.

The inventive choice according to the MP & MP * modalities, of a reactive aqueous emulsion (eg silicone), capable, by elimination of water (for example by drying - evaporation - activated or not and / or by absorption on the support) and optionally by crosslinking, to form an elastic bandage and self-adherent, provides all the advantages associated with the use of water as curable polymer transport fluid: safety, economy, ease of use (especially washing tools with water).

The biphasic aspect of the composition allows an association with both hydrophobic and hydrophilic phytosanitary active ingredients.

With regard to the MP * modality of the invention, one of the interesting advantages of the process is related to the water repellency of the silicone dressing used. This completes the barrier effect, which can be illustrated by specifying that such a dressing applied to wounds or in the hollows of plants or trees allows, preventively, to avoid the accumulation of stagnant water and the rotting of the plant. .

As already pointed out above, the elasticity is an asset for the dressing concerned by the process according to the invention. To go in this direction, it is entirely recommended according to the invention that the composition used is curable elastomer.

Treated plants can be sick, injured and / or pruned plants or trees.

Preferably, the silicone dressing is obtained by directly applying to the plant at least one layer of the composition (eg silicone) and allowing the layer to harden by drying and / or polymerization / crosslinking, so as to form a synthetic coating (eg silicone ) waterproof and adhering to the plant. This is therefore a coating of a silicone composition, for example pasty on the plant so as to form or build the dressing in situ.

Preferably, the functional additive (G) is chosen from the phytosanitary active principles of treatment and / or protection and / or growth aid (development) of plants. More particularly, this functional additive (G) is chosen from the group comprising: healing agents, fertilizers, bactericides, pesticides and their mixtures.

According to a remarkable characteristic of the invention, during application to the plant, the curable composition is a paste with a viscosity at 25 ° C. of between 1.10 ³ and 1.10 ⁷ mPa.s, preferably between 1.10 ⁴ and 1.10 ⁶ mPa. .s, and even more preferably between 1, 2.10 ³ and 5.10 ⁵ mPa.s. All the viscosities referred to herein correspond to a dynamic viscosity value at 25 ° C. called "Newtonian", that is to say the dynamic viscosity which is measured, in a manner known per se, at a gradient shear rate sufficiently low that the measured viscosity is independent of the velocity gradient. The term "paste" covers in particular precursors not yet hardened, in liquid, semi-liquid or semi-thick form. These precursors are advantageously ready for use. They can be applied easily in thin or thick layer (s), especially by spatula, brush, brush, roller or spray application.

Advantageously, the synthetic coating (for example gel or elastomer, in particular silicone) applied to the plant forms a dressing having excellent mechanical properties (including resistance / elasticity) self-adhesive and despite climatic variations. This method of application and the dressings it makes it possible to obtain is particularly suitable for plant supports to be treated and / or protected.

The ease of use which is one of the strong points of the invention is particularly noticeable in the preferred MP & MP * modalities which refer to so-called "aqueous" user-friendly technologies. In particular, a dispersion (e.g. silicone) aqueous is applicable quickly and safely, without special precautions.

Drying / crosslinking is done without the release of odor or toxic chemicals and cleaning tools is simply done with water. This aqueous dispersion does not contain volatile organic compounds. Finally, these benefits are acquired without harming the hardened dressing obtained after complete curing. In particular, this does not affect its mechanical properties, nor its ability to coat and marry perfectly the plant support and in particular the trees. The dressing is thus perfectly effective for phytosanitary treatment and protection. In addition to being easy to use, non-toxic and self-adhesive, the aqueous character of the dispersions (eg silicone) selected according to the preferred modalities MP & MP * has another significant advantage, the fact that the application tools can be easily cleaned with water until the dressing has set or hardened.

The dressing that can be obtained by the process of the invention in its particularly preferred mode MP * is advantageously constituted by an aqueous dispersion comprising at least one reactive silicone oil (A), at least one emulsifier (F) and at least one water (H). The optional ingredients of this dispersion are: at least one crosslinking agent (B) and / or at least one adhesion promoter (C) - preferably a silane (eg amine) - and / or at least one filler (D) (eg colloidal silicas or calcium carbonate) and / or at least one catalytic curing compound (E) and / or at least one functional additive (G). Such a dispersion is for example capable of forming at ambient temperature a gel or an elastomer, by elimination of water, namely drying and condensation of the reactive termini (for example silanols or optionally alkoxysilyl). As regards more particularly, but not exclusively, the process according to the invention in its MP * modality, the aqueous silicone dispersion used is monocomponent, which further facilitates the implementation.

One of the advantages of aqueous silicone dispersions according to MP * is related to the water-repellent properties of these polymers. The self-adhesive nature of the silicone coating (gel or elastomer) is particularly appreciable in this application.

Preferably, the silicone dispersion implemented in the MP * mode is free of solvents or volatile organic compounds.

More precisely, this aqueous silicone dispersion of the MP * mode is advantageously of the type of those described in the PCT application WO-A-02/00770 and in the application FR-A-2 861 722, the contents of which are integrated into the present invention. request by reference.

In the context of the present invention, however, it may be specified with regard to the oil (A) that the viscosity of its silicone phase (φ) is> 10 ⁴ mPa.s, preferably at 5.10 ⁴ mPa.s and more preferably still at 7.10 ⁴ mPa.s. The viscosity considered was determined for example using a Brookfield viscometer according to the AFNOR NFT76102 standard of

02/02/1972.

Advantageously, the oils (A) are α,> hydroxylated oils or functional oils comprising, per molecule, at least 2 condensable functional groups, optionally after hydrolysis.

More precisely, these oils (A) can be represented by the generic formula

(I) following:

^(I) (R ^J ) a R ¹ (R ^J ) a III

R ₃ - _{(a + b)} If O - (- Si O -) "- If R _{3- (a + b)}

(R ⁴ ) _b R "(R ⁴ ) _b

wherein: a is 0 or i, b is 0 or i, with a + b = 0; 1 or 2, n has a value sufficient to give the polymer of formula (a) the desired viscosity, the radicals R are identical or different and represent:

an OH group with a + b = 2;

an alkoxy or alkenyloxy group containing from 1 to 10 carbon atoms; an aryloxy group containing from 6 to 13 carbon atoms;

an acyloxy group containing from 1 to 13 carbon atoms;

a cetiminoxy group containing from 1 to 8 carbon atoms;

an amino or amido-functional group containing from 1 to 6 carbon atoms, linked to silicon by an Si-N bond; the radicals R ¹ and R ² are identical or different and represent aliphatic organic groups alkyl, alkenyl, having from 1 to 10 carbon atoms, phenyl aromatics, said groups being optionally substituted by halogen atoms or cyano groups; the radicals R ³ and R ⁴ are identical or different and represent alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl, aliphatic organic groups containing from 1 to 13 carbon atoms, aryl aromatics containing from 6 to 13 carbon atoms; at least two condensable functional groups optionally after hydrolysis being present per molecule of at least 80% of the radicals R ¹ to R ⁴ representing a methyl group.

By way of example of R radicals, mention may be made of the groups:

Alkoxy such as for example methoxy, ethoxy, octyloxy; Alkenyloxy such as for example vinyloxy, hexenyloxy, isopropenyloxy;

Aryloxy such as for example phenyloxy;

Acyloxy such as for example acetoxy;

• cetiminoxy such as for example ON = C (CH3) C2H5.

• aminofunctional such as for example ethylamino, phenylamino; Amidofunctional, such as, for example, methylacetamido;

Among the organic aliphatic or aromatic radicals mentioned above, mention may be made of:

R1, R4: for example, methyl, ethyl, octyl, trifluoropropyl, vinyl, phenyl; - R- *, R4: for example methyl, ethyl, octyl, vinyl, allyl, phenyl; - (CH ₂ ) ₃ -NH _2; - (CH ₂ ) 3-NH- (CH ₂ ) 2 -NH 2.

As concrete examples of D: R 1 R 1 SiC 2 units present in the oil (A), mention may be made of:

(CH ₃ ) ₂ SiO 2/2; CH ₃ (CH ₂ = CH) SiO ₂ Z ₂ ; CH ₃ (C ₆ H ₅ ) SiO ₂ Z ₂ ; (C ₆ H ₅ ) ₂ SiO _2/2 .

As concrete examples of M: RR ³ R ⁴ SiOy _{2 units,} mention may be made of: (CH ₃₎ 2 (OH) SiO _{/ 2;} (OCH ₃₎ 3 SiO _{/ 2;} [OC (CH 3) = CH ₂ ] 3 SiO _1/2 ;

(NH-CO-CH ₃ ) ₃ SiOy ₂ .

A crosslinking agent (B) is optionally used. In particular, this agent may be recommended when the oil (A) is an α, ω- (dihydroxy) polydiorganosiloxane polymer. Many crosslinking agents can be used in amounts that depend on their nature. These crosslinking agents are well known to those skilled in the art. The following is, by way of example, a list of crosslinking agents with the corresponding amounts recommended, expressed in parts by weight per 100 parts of oil (A): 0.5 to 10 parts of silicate of welded,

0.1 to 15 parts of an alkali metal organosiliconate (European Patent EP-B-266 729),

1 to 100 parts of a microemulsion of silsesquioxane resin (patents

US-B-3,355,406; US-B-3,433,780); 5 to 100 parts of a low molecular weight reactive silicone resin having alkoxy and acyloxy groups (US-B-4,554,187),

5 to 100 parts of a high-toluene-insoluble silicone resin (EP-A-304,719),

5 to 100 parts of a hydroxylated silicone resin composed of R units of formulas' ₃ SiO y ₂ (M) and / or 2 SiO _{_2/2} (D), associated with units of formulas R'SiO _{_3/2} (T ) and / or SiO 2 (Q), R 'being mainly a C 1 -C 6 alkyl, vinyl and 3,3,3-trifluoropropyl radical and a content by weight of hydroxyl group of between 0.1 and 10%. Among these resins, MQ, MDQ, TDM and TD resins (FR-A-2,638,166) may be mentioned in particular.

1 to 20 parts of a silane of formula: (R ") u Si X (4-u) in which R" is a monovalent organic radical, in particular methyl or vinyl, u is 1 or 0, X is a condensable and / or organic hydrolysable group of the same definition as the radical R of formula (I) above (alkoxy, alkenyloxy, acyloxy, cetiminoxy, alkylamino, alkylamido silanes described in particular in US Pat. No. 3,294,725; US-B 4,584,341; US-B-4,618,642; US-B-4,608,412; US-B-4,525,565; EP-B-387,157; EP-A-340,120; EP-A-364,375; FR-A 1,248,826; FR-AI 023 477.

By way of examples, mention may be made of the following alkoxysilanes:

If (OC ₂ H ₅ ) ₄ ; CH ₃ Si (OCH ₃ ) ₃ ; CH ₃ Si (OC ₂ Hs) ₃ ; (C ₂ H ₅ O) ₃ Si (OCH ₃ );

CH ₂ = CHSi (OCH ₃ ) ₃ ; CH ₃ (CH ₂ = CH) Si (OCH ₃ ) ₂ ; CH ₂ = CH (OC ₂ H ₅ ) ₃ ; CH ₂ = CHSi [ON = C (CH ₃ ) C ₂ H ₅ ]; CH ₃ Si [ON = C (CH ₃ ) ₂ ] ₃ . CH ₃ Si [-C (CH ₃ ) = CH ₂ ] ₃ ; methyltri (N-methylacetamidosilane); methyltris (cyclohéxylaminosilane).

Any adhesion promoters (C) are preferably silanes. These silanes (C) can be:

→ those constituted by by-products of synthesis reaction of the oils (A) and having the formula:

(R 5) _c Si (R) _{4 -} _c formula in which:

- ç is O; 1 or 2,

the radicals R 1, which are identical or different, correspond to the radicals R ³ and R ⁴ of the oil (A) of formula (I),

the radical R corresponds to the organic radical R of the polyorganosiloxane oil (A) of formula (I),

said silane being present in amounts of the order of from 0 to 10 parts by weight per 100 parts of oil (s) (A), and / or those belonging to the subgroup comprising: aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, glycidoxypropyltrimethoxysilane, optionally in their hydrolysed forms, and mixtures thereof, the promoters belonging to this subgroup being present in amounts up to 50% by weight of oil (s) (A);

And / or those chosen from silanes and / or hydroxylated water-bearing and carrier POSs, per molecule of at least one hydroxyl and at least one hydrophilic anchor-on-support function (Fas), as well as from mixtures of these products, preferably from hydroxylated linear hydroxylated polydiorganosiloxanes with siloxyl units D and / or MD and / or hydroxylated POS resins comprising siloxyl units T and optionally M and / or D and / or Q or else siloxyl units Q and M and / or D and / or T. These promoters (C) are free of Volatile organic compounds and are not substituted by hydrolysable organo-functional substituents. More specifically, examples of these promoters (C) include an organofunctional siloxane oligomer, free of alcohol and residual alkoxy groups, obtained by cohydrolysis of aminoethylaminopropyltriethoxysilane and methyltriethoxysilane and stripping of ethanol. This type of promoter is described in European Patent EP-BO 928 307.

According to a preferred arrangement of the invention, the optional charge (D) is selected from the group of hydrophilic compounds comprising: CaCO ₃ , SiO ₂ , TiO ₂ , Al ₂ O ₃ ZH ₂ O,

(co) organic polymer (s) in emulsion and mixtures thereof.

These hydrophilic compounds capable of constituting the particulate solid filler (D) can be obtained by precipitation in a liquid and / or by grinding.

In the case where it is particulate charge (D) obtained by precipitation, it is possible that the latter intervene in the water. An aqueous colloidal suspension of charge (D), which can be used for the preparation of the dispersion according to the invention, is then directly available.

According to one variant, this suspension can be obtained by incorporating the pulverulent dry charge (D) into the water. For example, slurries of precipitated CaCO ₃ or ground CaCO ₃ exist.

Silica SiO ₂ may be colloidal silica, precipitated silica or fumed silica.

The term "colloidal silica" refers to a stable suspension of differentially-sized, substantially spherical silica particles ranging in size from 0.00001 to 0.1 μm, preferably from 0.001 to 0.05 μm.

According to one variant, the dispersions used in the process according to the invention may comprise, in addition to the hydrophilic filler (D) supplied in the form of an aqueous colloidal suspension, a filler (D ') which is involved in the process of obtaining of the dispersion, in powder form. This charge (D ') brought into powder in the mixture leading to the dispersion is distinguished from the dry hydrophilic filler (D) through its reduced specific surface area Ss (m ² / g), namely: Ss <5 preferably Ss <3

As examples of pulverulent fillers (D '), mention may be made of: CaCO ₃ , SiO ₂ , TiO ₂ , Al ₂ O ₃ / H ₂ O.

Advantageously, the filler (D ') may represent 5 to 100 parts by dry weight per 100 parts by weight of silicone phase φs. Any catalytic hardening compounds (E) are well known to those skilled in the art; these are the carboxylic acid salts and metal halides such as, for example, lead, zinc, zirconium, titanium, iron, barium, calcium, manganese and especially tin. There may be mentioned: organic catalysts, such as amines or organic compounds functionalized with amines, reaction products of tin dicarboxylates (eg dibutyltin dilaurate) and ethyl polysilicate (US-A-3 862 919 ), chelates, especially tin bischelates (EP-A-147 323;

EP-A-235 049), diorganotin dicarboxylates (GB-A-1 289 900), alkoxides, or complexes. They can be used in amounts of up to about 3 parts by weight, preferably in the region of 0.05 to 1 part by weight per 100 parts of oil (A).

The emulsifiers (F) used may be ionic or non-ionic surfactants or water-soluble polymers. Preferably, they are nonionic surfactants. By way of examples, mention may be made of alkoxylated fatty acids, polyalkoxylated alkylphenols, polyalkoxylated fatty alcohols, polyalkoxylated or polyglycerolated fatty amides, polyglycerolated alcohols and alpha diols, ethylene oxide-propylene oxide block polymers, and alkylglucosides, alkylpolyglucosides, sucroethers, sucroesters, sucroglycerides, sorbitan esters and ethoxylated compounds of these sugar derivatives.

According to one variant, the emulsifiers (F) are selected from anionic surfactants such as, for example, alkylbenzene sulfonates, alkylsulphates, alkylethersulphates, alkylarylethersulphates, dioctylsulphosuccinates, and alkali metals. The (mixture of) emulsifier (s) is chosen according to the nature of the silicone oil (A) to be emulsified; an HLB of the order of 11 to 15 is generally chosen to emulsify a silicone oil (A) consisting of an α, ωbis (hydroxy) polydimethylsiloxane polymer. The weight ratio water / water + emulsifier (s) (F) is a function of the viscosity of the silicone phase (φs) and the nature of the (mixture of) surfactant (s); this ratio is for example of the order of 20/100 to 70/100, preferably of the order 25/100 to 60/100 to stabilize an emulsion of a silicone phase consisting of a α, o> dihydroxylated oil of viscosity on the order of 30 to 500 Pa.s, using a nonylphenol having 9 or 10 ethoxy units as sole emulsifier (F). In addition to the functional additives (G) consisting of phytosanitary active ingredients, the curable composition used may comprise other functional additives (I), including in particular plasticizers and / or salts and / or thickeners and / or charge dispersing agents, the latter being preferably selected from the group of products with hydrophilic function (s) anionic (s) and even more preferably from the group comprising polyacrylates and / or (poly) phosphates. These additives (I) may also or more precisely be: plasticizers, for example polydimethylsiloxane oils with a viscosity in the range of 300 to 10,000 mPa.s, dioctylphthalates, dialkylbenzenes optionally in aqueous emulsion, in amounts of from 0 to 70 parts by weight per 100 parts by weight of oil (A); thickening agents such as water-soluble polymers with a molecular mass greater than 10,000 g / mol, such as, for example, alkali metal polyacrylates, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidones, carrageenans, alginates, methylcelluloses and hydroxyalkylcelluloses; xanthan gum in amounts of up to 10% by weight of the final aqueous dispersion; charge dispersants such as, for example, alkali metal polyacrylates having a molecular weight of less than 5,000; inorganic phosphates in amounts of up to 10% by weight of the final aqueous dispersion; optionally inorganic or organic pigments in a quantity less than

4% preferably 2% by weight relative to the total mass of the dispersion. These additives may be introduced either into the silicone phase before it is emulsified or to the emulsion before dilution.

In practice, the silicone phase (φs) of the dispersion according to the MP * modality used in the surface treatment peculiar to the invention consists of: - (φs1) an oil (A) with a viscosity of at least 10 ⁴ mPa .s,

- (φs2) a mixture of oils (A), a viscosity mixture at least equal to 10 ⁴ mPa.s,

- (φs3) a mixture of at least one oil (A) and at least one crosslinking agent (B) if this is necessary and / or an adhesion promoter (C) - for example a silane -, mixture of viscosity of at least 10 ⁴ mPa.s, - or (φs4) a mixture of at least one oil (A) and a possible catalytic compound

(E), optionally in the presence of at least one adhesion promoter (C) - for example a silane -. With regard to the preparation of the silicone aqueous dispersion selected according to the MP * modality of the invention, reference is made for more details in PCT application WO-A-02/00770 and FR-A-2 861 722.

Advantageously, the aqueous silicone dispersion A (B) (C) (D (E) F (G) H (I) a -les () denotes the optional components:

A dry extract comprised between 50 and 95%, preferably between 60 and 90, and even more preferentially between 75 and 85%,

And a pH of between 7 and 12, preferably between 8 and 12 and, more preferably, between 10 and 11.

According to another of its aspects, the subject of the invention is a silicone composition that can be used for the treatment and / or the protection of a plant, which is extensible, curable and comprises at least one aqueous dispersion of silicone oil (s) comprising: A-100 parts by weight of at least one polyorganosiloxane oil (A) capable of condensation-curing, if necessary in the presence of a crosslinking agent (B), of an elastomer; If necessary, from 0.1 to 10 parts by weight of at least one crosslinking agent

Advantageously, this composition is characterized in that it comprises from 0.01 to 10, preferably from 0.1 to 5% by weight, of phytosanitary functional additive (G) chosen from the group comprising: cicatrization agents, fertilizers, bactericides, pesticides and their mixtures.

The invention also covers, as new product, any article, in particular a dressing, that can be used for the treatment and / or protection of a plant, characterized in that it is obtained by hardening of the curable composition (eg silicone) as defined above. Such an article, particularly a dressing, is advantageously self-adhesive especially on plants.

The invention can find many applications in arboriculture, horticulture, gardening, vine ...

The examples are given for information only and can not be considered as a limit of the scope and spirit of the invention.

EXAMPLES

Example 1: RHODORSIL® 3000 elastomer-based protective dressing.

1.1 / The aqueous silicone dispersion (ABCDEFGHD crosslinkable used is that marketed under the name RHODORSIL® 3000 by the company RHODIA SILICONE:

Α, ω hydroxylated polydimethylsiloxane oil having a viscosity of 135,000 mPa.s,

2. polydimethylsiloxane oil blocked with methyl groups of viscosity 100 mPa.s, -B- hydroxylated MDT resin with a viscosity of 1000 mPa.s (containing 0.5% by weight of hydroxyl groups, 62% by weight of trifunctional units, 24% by weight) of di-functional units and 14% by weight of mono-functional units), -C-aqueous solution containing 77% by weight of a resin T (OH) aminated with aminopropyl groups marketed by WITCO under the name VS 142. -D-

1. V5639 precolor pigment marketed by Wϋnsiedel predispersed in an additive (I) sodium polyacrylate-dispersant marketed by Coatex under the name Coatex P50 or by Protex under the name Prox Al 1

2. Crushed calcium carbonate marketed by OMYA under the name BLR3 and 186.9 g of precipitation carbonate sold by SOLVAY under the name Socal 312, with stirring at 100 rpm. -E- 60% solution by weight of dioctyltin dilaurate -F-

Rhodasurf® ROX (85% aqueous solution of a polyethoxylated C ₁₃ aliphatic alcohol containing about 8 oxyethyl units) -G-antifungal

-H- demineralized water.

Characteristics of the aqueous dispersion: dry extract of approx. 80%, pH = 10.5

1.21 Implementation of the Process According to the Invention

The aqueous silicone dispersion according to 1.1 / (or RHODORSIL® 3000 putty) is used as it is, without addition of additional ingredient and without dilution.

A film about 2 mm thick (after drying) is produced by spreading the RHODORSIL® 3000 putty with a doctor blade 3 mm thick, on a non-stick paper, then let it dry in the conditioned room ( at 50% relative humidity and 23 ° C). The elastomer thus obtained has a hardness of 18 Shore A (measured on 3 stacked pieces of film).

Example 2: The dispersion 1.1. RHODORSIL® 3000 + healing additive (G) (indole acetic acid)

Preparation of an aqueous solution of indole acetic acid: in a 60 ml glass flask, 0.6 g of indolacetic acid-3 (powder reference 1.00353.0010 from Merck), 1.7 g of water are weighed out demineralized and 3 g of Degussa DSl 151 (aqueous silane amino solution). After stirring for a few minutes using a magnetic stirrer, at room temperature, a homogeneous solution is obtained.

Incorporation in the aqueous dispersion RHODORSIL® 3000: in a plastic container: introduction of 60 g of RHODORSIL® 3000 followed by 5.3 g of indole acetic acid (growth hormone) solution. The mixture is produced by passing for 20 seconds in a Speed-mixer (centrifugal stirrer type DAC 150 FVK from the company HAUSCHILD) at a speed of 1000 rpm.

The concentration of indole acetic acid in the RHODORSIL® 3000 aqueous dispersion is 0.9%. Good compatibility is observed between the binder formed by the RHODORSIL® 3000 aqueous dispersion and the healing additive (G). The final mixture has the same appearance as the initial RHODORSIL® 3000 dispersion (cream smooth and unctuous, without defects or grains), and after 7 days of drying under 2 mm (at 23 ° C and 50% relative humidity) we obtain the same hardness: 18 Shore A.

It has been verified that the wood adhesion properties of the RHODORSIL® 3000 aqueous dispersion are not disturbed by the addition of the healing agent.

Example 3: The dispersion 1.1. aqueous RHODORSIL® 3000 + additive (G) biocide (bactericide and fungicide)

3.1 - The aqueous dispersion RHODORSIL® 3000 + additive (G) biocide: ECOFILM® OTI:

In a plastic container, introduction of 60 g of RHODORSIL® 3000 aqueous dispersion followed by 0.66 g of ECOFILM® OTI (biocide based on a combination of 3-iodo-2-propynyl-n-butylcarbamate and 2- octyl-2H-isothiazol-3-one, marketed by the company PROGIVEN).

The mixture is made by passing for 20 seconds in a mixer-mixer (centrifugal stirrer) at a speed of 1000 rpm.

The concentration of ECOFILM® OTI in the RHODORSIL® 3000 aqueous dispersion is approximately 1.1%

Good compatibility is observed between the binder formed by the aqueous dispersion RHODORSIL® 3000 and the additive (G) biocide. The final mixture is slightly granular, but after 7 days of drying under 2 mm (at 23 ° C. and 50% relative humidity) a good uptake of the product is observed and the same hardness is obtained: 18 Shore A.

The adhesion properties on wood are not disturbed. 3.2 - The aqueous dispersion RHODORSIL® 3000+ additive (G) biocide: ECOBOIS®:

In a plastic container introduction of 60 g of the aqueous dispersion RHODORSIL® 3000 and 0.9 g of ECOBOIS (biocide and more specifically Fungicide based on 3-iodo-2-propynyl-n-butylcarbamate, marketed by the company PROGIVEN).

The ECOBOIS concentration in the RHODORSIL® 3000 aqueous dispersion is about 1.5%

Good compatibility is observed between the binder formed by the aqueous dispersion RHODORSIL® 3000 and the additive (G) biocide. The final mixture has the same appearance as the initial aqueous dispersion RHODORSIL® 3000 (cream smooth and unctuous, without defects or grains), and after 7 days of drying under 2 mm (at 23 ° C and 50% relative humidity) we obtain the same hardness: 18 Shore A.

The adhesion properties on wood are not disturbed.

Example 4: Dispersion application tests 1.1. RHODORSIL® 3000 on trees

The applications were carried out on apple, quince, plum, mirabelle plum and pear trees with the RHODORSIL® 3000 aqueous dispersion without dilution with a spatula (or coating knife) and without adding any additives. The dressings with the RHODORSIL® 3000 aqueous dispersion appear on the two attached photos

(see Figures 1 and 2) in which the cured silicone dressings are designated by the letter (P).

The product is easy to apply to wood regardless of substrate moisture and adheres well.

It allows: • to protect the plants whose bark has been torn off

• facilitate the healing of cut branches,

• to plug cankers (common especially on apple trees),

• to plug cavities colonized by insects, larvae ...., • fill hollow parts (forks, branch branches) that can accumulate water that favors decay.

It has been found that these coatings accompany the growth of the tree and come off naturally after 1 to 3 years.

Claims

1) Process for treating and/or protecting a plant, characterized in that it essentially consists of applying to the plant, at least one dressing obtained from a composition - preferably polymer - which can be cured either under the effect of drying, either by chemical crosslinking, or by drying and chemical crosslinking, in particular at room temperature, in a preventive and/or curative synthetic coating of the silicone sealant type.

2) Method according to claim 1, characterized in that the curable composition comprises at least one aqueous dispersion - preferably polymer - curable by elimination of water.

3) Method according to claim 2, characterized in that the dispersion is an aqueous dispersion of silicone oil(s) comprising:

-A- 100 parts by weight of at least one polyorganosiloxane oil (A) capable of crosslinking by condensation, if necessary in the presence of a crosslinking agent (B), into an elastomer;

-B- if necessary, from 0.1 to 10 parts by weight of at least one crosslinking agent (B);

-C- optionally, up to 10 parts by weight of at least one adhesion promoter (C) -preferably a silane-;

-D- optionally, up to 200 parts by dry weight of a charge (D); -E- optionally, a catalytically effective quantity of at least one catalytic hardening compound (E) of up to 3 parts by weight;

-F- at least one emulsifier (F); -G- optionally at least one functional additive (G) for plant treatment and/or protection; -H- and water.

4) Method according to any one of the preceding claims, characterized in that, when applied to the plant, the curable composition is a paste with a viscosity at 25°C between 1.10 ³ and 1.10 ⁷ mPa.s, of preferably between 1.10 ⁴ and 1.10 ⁶ mPa.s, and, even more preferably between 1.2.10 ³ and 5.10 ⁵ mPa.s.

5) Method according to any one of the preceding claims, characterized in that the dressing is obtained by applying directly to the plant at least one layer of the curable composition and allowing this layer to harden by drying and polymerization/crosslinking, so as to form a waterproof synthetic coating adhering to the plant.

6) Method according to claim 3, characterized in that the functional additive (G) for treatment and/or protection of the plant is chosen from the group comprising: healing agents, fertilizers, bactericides, pesticides and their mixtures.

7) Method according to claim 5, characterized in that the synthetic coating applied to the plant is ensured to form a self-adhesive and elastic dressing.

8) Method according to any one of claims 3 to 7, characterized in that the oils (A) are α, ω-hydroxylated oils or functional oils comprising per molecule at least 2 functional groups possibly condensable after hydrolysis.

9) Method according to claim 3 or 8, characterized in that the oils (A) have the generic formula (I)

(R% R ¹ (R% III

R ₃ -(a ₊ b) If O —("Si O -)„— If R _3- (a ₊ b)

(R ⁴ ) _b Ff (R ⁴ ) _b formula in which: - a is 0 or i,

- b is O or 1,

- with a+b = 0; 1 or 2,

- n has a sufficient value to give the polymer of formula (a) the desired viscosity, - the radicals R are identical or different and represent:

- an OH group with a+b = 2;

- an alkoxy or alkenyloxy group containing 1 to 10 carbon atoms;

- an aryloxy group containing 6 to 13 carbon atoms;

- an acyloxy group containing 1 to 13 carbon atoms; - a ketiminoxy group containing 1 to 8 carbon atoms;

- an amino- or amido-functional group containing 1 to 6 carbon atoms, linked to silicon by an Si-N bond; the radicals R ¹ and R ² are identical or different and represent organic aliphatic alkyl, alkenyl groups, having from 1 to 10 carbon atoms, aromatic phenyl, said groups being optionally substituted by halogen atoms or cyano groups; - the radicals R ³ and R ⁴ are identical or different and represent aliphatic organic alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl groups, containing from 1 to 13 carbon atoms, aromatic aryl groups containing from 6 to 13 carbon atoms; at least 2 functional groups possibly condensable after hydrolysis being present per molecule.

10) Method according to claim 9, characterized in that at least 80% of the radicals R ¹ to R ⁴ representing a methyl group.

11) Method according to claim 3, characterized in that the crosslinking agent (B) is sodium silicate, an alkali metal organosiliconate, a microemulsion of silsesquioxane resin, a low molecular weight reactive silicone resin having alkoxy groups and acyloxy, a high mass silicone resin insoluble in toluene, a hydroxylated silicone resin, an alkoxysilane, an alkylaminosilane, an alkylamidosilane.

12) Method according to claim 3, characterized in that the adhesion promoter, preferably silane (C), is chosen from:

→ those consisting of oil synthesis reaction by-products (A) and having the formula:

(R5) _c If (R) ₄ _ _c formula in which:

- it is O;1 or 2,

- the radicals R^, identical or different, correspond to the radicals R ³ and R ⁴ of the oil (A) of formula (I),

- the radical R corresponds to the organic radical R of the polyorganosiloxane oil (A) of formula (I),

- said silane being present in quantities of the order of 0 to 10 parts by weight per 100 parts of oil(s) (A). → and/or those belonging to the subgroup comprising: aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, glycidoxypropyl-trimethoxysilane, optionally in their hydrolyzed forms, and their mixtures, promoters belonging to this subgroup being present in quantities of up to 50% of the weight of oil(s) (A);

→ and/or those chosen from silanes and/or water-soluble and carrier hydroxylated POS, per molecule of at least one hydroxyl and at least one hydrophilic anchoring function on support (Fas), as well as from mixtures of these products, preferably among linear hydroxylated polydiorganosiloxanes with D and/or MD siloxyl units and/or hydroxylated POS resins comprising T and optionally M and/or D and/or Q siloxyl units or even Q and M siloxyl units and/or D and/or T.

13) Method according to any one of preceding claims 3 to 12, characterized in that the filler (D) is selected from the group of hydrophilic compounds comprising: CaCO ₃ , SiO ₂ , TiO ₂ , Al ₂ O ₃ ZH ₂ O , organic (co)polymer(s) in emulsion and their mixtures.

14) Method according to any one of preceding claims 3 to 13, characterized in that the catalytic hardening compound (E) is a tin derivative, used in quantities which can range from 0.05 to 1 part by weight per 100 parts of oil (A).

15) Method according to any one of preceding claims 3 to 14, characterized in that the aqueous dispersion is chosen such that its silicone phase (φs) consists of:

- (φsl) an oil (A) with a viscosity at least equal to 10 ⁴ mPa.s, - (φs2) a mixture of oils (A), mixture with a viscosity at least equal to 10 ⁴ mPa.s,

- (φs3) a mixture of at least one oil (A) and at least one crosslinking agent (B) if this is necessary and/or an adhesion promoter (C) - for example a silane -, mixture with viscosity of at least 10 ⁴ mPa.s,

- or (φs4) a mixture of at least one oil (A) and a possible catalytic compound (E), possibly in the presence of at least one adhesion promoter (C) - for example a silane -.

16) Method according to claim 3 to 15, characterized in that the aqueous silicone dispersion has: “a dry extract of between 50 and 95%, preferably between 60 and 90, and even more preferably between 75 and 85%,

• and a pH between 7 and 12, preferably between 8 and 12 and, even more preferably, between 10 and 11. 17) Silicone composition usable for the treatment and/or protection of a plant, extendable, hardenable and comprising at least one aqueous dispersion of silicone oil(s) comprising: -A- 100 parts by weight of at least one oil polyorganosiloxane (A) capable of crosslinking by condensation, if necessary in the presence of a crosslinking agent (B), into an elastomer; -B- if necessary, from 0.1 to 10 parts by weight of at least one crosslinking agent

(B); -C- optionally, up to 10 parts by weight of at least one adhesion promoter (C) -preferably a silane-;

-D- optionally, up to 200 parts by dry weight of a charge (D); -E- optionally, a catalytically effective quantity of at least one catalytic hardening compound (E) of up to 3 parts by weight; -F- at least one emulsifier (F);

-G- at least one functional additive (G) for plant treatment and/or protection; -H- and water.

18) Composition according to claim 16, characterized in that it comprises from 0.01 to 10, preferably from 0.1 to 5% by weight of functional additive (G) chosen from the group comprising: healing agents , fertilizers, bactericides, pesticides and their mixtures.

19) Article, in particular dressing, capable of being used for the treatment and/or protection of a plant, characterized in that it is obtained by hardening of the composition as defined in claims 1 to 18.

20) Article, in particular dressing, according to claim 19, characterized in that it is self-adhesive in particular on plants.