WO1999025193A1 - Synergetic fungicidal and/or bactericidal composition - Google Patents

Abstract

The invention concerns a synergetic fungicidal and/or bactericidal composition comprising dodine and a phosphorous acid derivative, and a method for fighting against, curing or preventing phytopathogenic fungi and/or bacteria using such a composition.

Description

 Synergistic fungicidal and / or bactericidal composition.

The subject of the present invention is a synergistic fungicidal and / or bactericidal composition comprising dodin and a derivative of phosphorous acid and a process using said composition and intended to protect, for curative or preventive purposes, cultures against fungal attacks .

It is always desirable to improve the spectrum of activity and the effectiveness of such fungicidal compounds, or to reinforce them by combining them with other molecules in order to obtain a more effective product (association with a systemic fungicide, these fungicides being rather molecules of the "contact" type) or else to prevent the appearance of fungal strains resistant to these new fungicides.

It is also very desirable to have fungicidal products benefiting from an improved persistence of action, so as to space over time the number of phytosanitary treatments necessary for good pest control.

In all cases, it is particularly advantageous to be able to reduce the quantity of chemicals spread in the environment, while ensuring effective protection of crops against fungal attacks.

It has now been found that one (or more) of the foregoing objectives can be achieved by the fungicidal and / or bactericidal composition according to the present invention.

The present invention therefore relates primarily to a synergistic fungicidal and / or bactericidal composition comprising as compound A dodin, also called dodecylguanidine monoacetate, and at least one fungicidal compound B chosen from the group comprising phosphorous acid derivatives as metallic phosphites such as fosetyl-Al, and phosphorous acid itself and its alkali or alkaline earth salts.

The fungicidal and / or bactericidal composition according to the invention advantageously comprises the components A and B in a weight ratio A / B of between 1/12 and 8/1, preferably between 1/6 and 3/1, and so even more advantageous in a ratio between 1/3 and 3/4. It is understood that said fungicidal and / or bactericidal composition may contain a single compound B or more of such a compound, for example 1. 2 or 3 compounds B depending on the use for which it is intended.

Among the more especially preferred meanings of compound B defined above, fosetyl Al is still more preferred. In a perfectly unexpected manner, the composition according to the invention then significantly improves the action of the active ingredients taken separately for a number of fungi particularly harmful to crops, such as in particular the vine or solanaceae. This improvement is reflected in particular by a reduction in the doses of each of the constituents, which is particularly advantageous for the user and the environment. The fungicidal and / or bactericidal product (mixture) thus exhibits synergistic properties attested by the application of the method defined by

Limpel, L.E., P.H. Schuldt and D. Lammont, 1962, Proc. NEWCC 16: 48-53. using the following formula, also called Colby's formula:

E = X + Y - X. Y / 100

in which:

- E is the expected percentage inhibition of the growth of the fungus by a mixture of the two fungicides A and B at defined doses, respectively equal to a and b;

- X is the percentage of inhibition observed by the fungicide and / or bactericide A at dose a,

- Y is the percentage of inhibition observed by the fungicide and / or bactericide B at dose b.

When the percentage of inhibition observed of the mixture is greater than E, there is synergy.

Preferably, when component B is fosetyl-Al, the A / B ratio is between 1/6 and 3/1, and even more advantageously this ratio is between 1/3 and 3/4 and quite preferably this ratio is equal to 1/2 for all of the crops envisaged.

The structures corresponding to the common names of the active ingredients A and B are indicated in at least one of the following 2 works: - "The pesticide manual" edited by Clive TOMLIN and published by the British Crop Protection Council. 10th edition (pages 382 and 530);

- the 1994 Phytosanitary Index, published by the Association for Agricultural Technical Coordination, 30th edition.

The fungicidal and / or bactericidal composition according to the invention comprises, as active material, a compound A and at least one compound B in admixture with solid or liquid carriers, acceptable in agriculture and / or surfactants also acceptable in agriculture . In particular, the usual inert supports and the usual surfactants can be used. These compositions cover not only the compositions ready to be applied to the culture to be treated by means of a suitable device, such as a spraying device, but also the concentrated commercial compositions which must be diluted before application to the culture. The term active ingredient denotes the combination of at least one compound A with at least one compound B.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestrants, etc. More generally compounds A and B can be combined with any solid or liquid additive corresponding to the usual techniques of formulation.

In general, the compositions according to the invention usually contain from 0.05 to 95% (by weight) of active material, one or more solid or liquid supports and, optionally, one or more surfactants.

By the term "support", in the present description, is meant an organic or mineral, natural or synthetic material, with which the active material is combined to facilitate its application to the aerial parts of the plant. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, in particular butanol etc.).

The surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of poly acrylic acids, of salts lignosulfonic acids, salts of ulfonic or naphthalenesulfonic phenol acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of esters of sulfosuccinic acids, derivatives of taurine (in particular alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of fatty acids and of polyols, derivatives with a sulfate function, sulfonates and phosphates of the foregoing compounds. The presence of at least one surfactant is generally essential when the active material and / or the inert support are not soluble in water and the vector agent for the application is water.

Thus, the compositions for agricultural use according to the invention can contain the active material within very wide limits, ranging from 0.05% to 95% (by weight). Their content of surfactant is advantageously between 5% and 40% by weight. Unless otherwise indicated the percentages given in this description, including the claims, are by weight.

These compositions according to the invention are themselves in fairly diverse forms, solid or liquid.

As forms of solid compositions, mention may be made of dusting powders (with an active ingredient content of up to 100%) and granules. in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of active material in these granules being between 0.5 and 80% for the latter cases), the tablets or effervescent tablets.

The fungicidal and / or bactericidal composition according to the invention can also be used in the form of powders for dusting; one can also use a composition comprising 50 g of active material and 950 g of talc; one can also use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powder to spray), pasta, gels. The concentrated suspensions, applicable in spraying, are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0, 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for water.

As an example, here is a concentrated suspension composition:

Example SC 1:

- active ingredient 500 g

- polyethoxylated tristyrylphenol phosphate 50 g

- polyethoxylated alkylphenol 50 g

- sodium polycarboxylate 20 g

- ethylene glycol 50 g

- organopolysiloxane oil (defoamer)

- polysaccharide 1.5 g

- water 316.5 g

Wettable powders (or spray powder) are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0 to 30% of a wetting agent, 3 20% of a dispersing agent, and, when necessary, 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, dyes, etc. To obtain the spraying powders or wettable powders, the active materials are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other suitable grinders. This gives sprayable powders whose wettability and suspension are advantageous; we can suspend them with water at any desired concentration and these suspensions can be used very advantageously in particular for application to the leaves of plants.

Instead of wettable powders, pasta can be made. The conditions and methods of making and using these pastes are similar to those of wettable powders or spraying powders.

As an example, here are various compositions of wettable powders (or spraying powders):

Example PM 1 - active ingredient 50%

- ethoxylated fatty alcohol (wetting agent) 2.5%

- ethoxylated phenylethylphenol (dispersing agent) 5%

- chalk (inert support) 42.5%

Example PM 2:

- active ingredient 10%

- branched type oxo synthetic alcohol, C13 ethoxylated with 8 to 10 ethylene oxide

(wetting agent) 0.75% - neutral calcium lignosulfonate (dispersing agent) 12%

- calcium carbonate (inert filler) q.s.p. 100%

Example PM 3: This wettable powder contains the same ingredients as in the previous example, in the following proportions:

- active ingredient 75%

- wetting agent 1.50%

- dispersing agent 8% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 4:

- active ingredient 90%

- ethoxylated fatty alcohol (wetting agent) 4% - ethoxylated phenylethylphenol (dispersing agent) 6% Example PM 5:

- active ingredient 50%

- mixture of anionic and nonionic surfactants (wetting agent) 2.5%

- sodium lignosulfonate (dispersing agent) 5%

- kaolin clay (inert support) 42.5%

The aqueous dispersions and emulsions, for example the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise". The fungicidal compositions according to the invention can be formulated in the form of water-dispersible granules also included within the scope of the invention.

These dispersible granules, of apparent density generally comprised between approximately 0.3 and 0.6 have a particle size generally comprised between approximately 150 and 2000 and preferably between 300 and 1500 microns.

The active material content of these granules is generally between approximately 1% and 90%, and preferably between 25% and 90%.

The rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the selected filler is soluble or not in water. When the filler is water-soluble, it can be mineral or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as for example kaolin or bentonite. It is then advantageously accompanied by surfactants (at a rate of 2 to 20

% by weight of the granule) of which more than half is, for example, constituted by at least one dispersing agent, essentially anionic, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline earth lignosulfonate, the rest being constituted by nonionic or anionic wetting agents such as an alkali or alkaline earth alkylnaphthalene sulfonate. Furthermore, although this is not essential, other adjuvants can be added such as anti-foaming agents.

The granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above. It is also possible to use granules obtained as above and then impregnated with a composition containing the active material.

Preferably, it is obtained by extrusion, operating as indicated in the examples below.

Example GD 1: Dispersible granules

In a mixer, 90% by weight of active material and 10% urea pearls are mixed. The mixture is then ground in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granule is obtained which is dried, then crushed and sieved, so as to keep respectively only the granules of a size between 150 and 2000 microns.

Example GD2: Dispersible granules

In a mixer, the following constituents are mixed:

- active ingredient 75%

- wetting agent (sodium alkylnaphthalene sulfonate) 2%

- dispersing agent (sodium polynaphthalene sulfonate) 8% - inert filler insoluble in water (kaolin) 15%

This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between 0.15 and 0.80 mm. These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions. As regards the compositions suitable for storage and transport, they more advantageously contain from 0.5 to 95% (by weight) of active material.

Another subject of the invention is a method of combating, for curative or preventive purposes, against phytopathogenic fungi of cultures and / or bacteria, characterized in that an effective and non-phytotoxic amount of a combination of compound A and at least one compound B, for example in a fungicidal and / or bactericidal composition according to the invention. The phytopathogenic fungi of cultures which can be combated by this process are in particular those:

- from the oomycetes group:

- of the genus Phytophthora such as Phytophthora phaseoli, Phytophthora citrophthora, Phytophthora capsici, Phytophthora cactorum, Phytophthora palmivora, Phytophthora cinnamoni, Phytophthora megasperma,

Phytophthora parasitica, Phytophthora fragariae, Phytophthora cryptogea, Phytophthora porri, Phytophthora nicotianae, Phytophthora infestans (late nightshade, especially potato or tomato);

- from the Peronosporaceae family, in particular Plasmopara viticola (downy mildew), Plasmopara halstedei (sunflower downy mildew), Pseudoperonospora sp (especially cucurbit downy mildew (Pseudoperonospora cubensis) and hops (Pseudoperonospora humuli), mildew lettuce), Peronospora tabacinae (downy mildew), Peronospora destructor (onion downy mildew), Peronospora parasitica (downy mildew), Peronospora farinosa (endive mildew and beet mildew).

- from the adelomycetes group:

- of the genus Alternaria, for example Alternaria solani (alternaria of solaneas, and in particular of tomatoes and potatoes),

- of the genus Guignardia, in particular Guignardia bidwellii (black rot of the vine),

- of the genus Venturia, for example Venturia inaequalis, Ventu a pirina (apple or pear scab),

- of the genus Taphrina, for example Taphrina deformans (peach blister). Diseases of bacterial origin that can be combated by this process include:

- fire blight, erwinia amylovora;

- the bacterial spot of stone fruit trees, xanthomonas campestris;

- bacteriosis of the pear tree, pseudomonas syringae.

The crops envisaged in the context of the present invention are preferably vegetable crops (beans, onions, cucurbits, cabbage, potatoes, tomatoes, peppers, spinach, peas, lettuce, celery, endives), fruit crops (strawberries, raspberries), tree crops (apple, pear, cherry, ginseng, lemon, coconut, pecan, cocoa, walnut, rubber, olive, poplar, banana), vines, sunflowers, beets, tobacco and ornamental crops.

A classification made no longer by targeted fungi or bacteria but by target cultures can be illustrated as below:

- vine: powdery mildew (Uncinula necator), downy mildew (Plasmopara viticola), excoriosis (Phomopsis viticola) and black-rot (Guignardia bidwelliï), - vegetable crops: mildious (Peronospora sp., Bremia lactucae,

Pseudoperonospora sp),

- arboriculture: scab (Venturia inaequalis, V. pirina), bacterial diseases (erwinia amylovora, xanthomonas campestris, pseudomonas syringae), - citrus: scab (Elsinoe fawcetti), melanosis (Phomopsis citri) and Phytophthora sp diseases.

The fungicidal and / or bactericidal composition which is the subject of the invention is applied by means of various treatment methods such as: - spraying the aerial parts of the cultures to be treated with a liquid comprising said composition,

- dusting, incorporating granules or powders into the soil, watering, injecting into trees or painting.

Spraying a liquid on the aerial parts of the crops to be treated is the preferred treatment method. By "effective and non-phytotoxic amount" means an amount of composition according to the invention sufficient to allow the control or destruction of fungi or bacteria present or likely to appear on crops, and causing no symptoms for said crops notable phytotoxicity. Such an amount is likely to vary within wide limits depending on the fungus or bacteria to be combated, the type of culture, the climatic conditions, and the compounds included in the fungicidal and / or bactericidal composition according to the invention. This quantity can be determined by systematic field tests, within the reach of those skilled in the art.

The doses of use during the implementation of the method according to the invention will generally then be on vines, vegetable crops, arboriculture, citrus fruits, etc.: by foliar treatment: 500 to 6000 g ha of compound B, eg. fosetyl-Al, + 500 to 4000 g / ha of compound A and more precisely 1000 to 3000 g / ha + 500 to 3000 g / ha, or a total dose of composition according to the invention of between 1000 and 10000 g / ha, preferably between 1500 and 6000 g ha. Preferably, 1200 to 1800 g / ha of compound B and 600 to 900 g / ha of compound A are used, ie a total dose of composition according to the invention of between 1800 g / ha and 2700 g / ha.

Quite advantageously, 675 g / ha of compound A is used + 1350 g / ha of compound B (ratio 1/2), or in total 2025 g / ha.

Finally, the invention relates to a product comprising at least one compound A and at least one compound B for the control of phytopathogenic fungi and / or bacteria of a medium by simultaneous, sequential or separate application.

The following example is given purely by way of illustration of the invention, which it does not limit in any way.

Example: Combination of fosetyl-Al and dodine in the fight against apple scab.

The products tested are: Aliette WG: WG formulation containing 800g of fosetyl-Al / kg,

Syllit Flo: SC formulation containing 400g of dodin / 1.

The compositions tested are as follows: Aliette at the doses of 169, 337, 675 and 1350 g of active material (a.m.) / ha,

Syllit at doses of 84, 169, 337 and 675g of active ingredient (a.m.) / ha, Syllit + Aliette at doses of 84 + 169, 169 + 337, 337 + 675 and 675 + 1350g of m. at. (ratio l / 2) / ha.

Apple plants (var. Golden x Idared) 4 weeks old (stage

4-5 leaves) are inoculated with an aqueous suspension containing 150,000 spores of Venturia inaequalis / ml. The plants are placed in a climatic chamber at 16-18 ° C, 100% relative humidity (RH) under artificial light for 40 hours then are treated with the fungicidal compositions at the doses mentioned above (20 repetitions / dose) under a porridge volume of 5001 / ha. After drying the treatment, the plants are again replaced in a climatic chamber at 16-18 ° C, 100% RH, under artificial light and then at 85% RH from the 5th day after inoculation.

The disease is scored 17 days after inoculation. This consists of estimating:

- either the percentage of contaminated leaf area on the two most sensitive leaves of the plants,

- either the number of leaves contaminated with scab,

and, by comparison with an untreated-contaminated control, to define the percentage of effectiveness according to the following formula:

% practical efficiency = 100 x (% control contamination -% test contamination) /% control contamination

The results in terms of effectiveness (attack intensity) are presented in FIG. Effect on disease intensity

97 98

100 - 89

77

80 69

64 o 60 55 51 ϋ 48

£ 40

40 31 27

20 t

Dodine (EXP10343A) i fosetyl-Al (Aliette WG)! Dodine + fosetyl-Al

0> a a, u. o σ> t ^ w o

00 (O co ι> - (O O 1 * "in (O O r ^ m co ta O (O o" r- CO (O o

+ + * in r- + +

00 (O co un co

__

Doses (in g / ha)

Figure la: action of fosetyl-Al associated with dodine in the curative fight against apple scab; effect on attack intensity.

The association allows us to envisage a clear reinforcement of the curative action since with 337g of dodine associated with 675g of fosetyl-Al we obtained an action greater than what we had with 675g of dodine alone.

The results in terms of effectiveness (frequency of attack) are presented in FIG.

Effect on attack frequency

Doses (in g / ha) Figure lb: action of fosetyl-Al associated with dodine in the curative fight against apple scab; effect on attack frequency.

When we talk about frequency of appearance rather than intensity of attack of scab, the advantage of the association of fosetyl-Al with dodine is even more clearly highlighted.

By using Colby's formula, we determine the presence of synergy. The results are shown in Table 1 below.

Application rates (g / ha) Effect on intensity Effect on frequency 84 + 169 +11 +13 169 + 337 - 10 +19 337 + 675 +15 +37 675 + 1350 +1 +12

Table 1: synergy study between fosetyl-Al and dodine. Test 1.

Overall, a clear synergistic action is noted. It is more evident in the case of the effect of the mixture on the frequency of onset of the disease than on the intensity of attack.

Claims

1. A synergistic fungicidal and / or bactericidal composition comprising as compound A dodin and at least one fungicidal compound B chosen from the group comprising phosphorous acid derivatives such as metal phosphites such as fosetyl-Al, and phosphorous acid itself and its alkali or alkaline earth salts; said composition comprising components A and B in an A / B weight ratio of between 1/12 and 8/1, preferably between 1/6 and 3/1. 2. A fungicidal and / or bactericidal composition according to claim 1 characterized in that the compound B is fosetyl Al. 3. fungicidal and / or bactericidal composition according to one of claims 1 or 2, characterized in that the A / B ratio is between 1/6 and 3/1, and even more advantageously this ratio is between 1 / 3 and 3/4 and quite preferably this ratio is equal to 1/2 for all of the cultures envisaged. 4. fungicidal and / or bactericidal composition according to any one of claims 1 to 3, characterized in that it comprises compounds A and B in admixture with solid or liquid carriers acceptable in agriculture and / or surfactants also acceptable in agriculture. 5. A fungicidal and / or bactericidal composition according to any one of claims 1 to 4, characterized in that it comprises from 0.05 to 95% (by weight) of active material. 6. Method for controlling phytopathogenic fungi or bacteria in a medium, characterized in that a compound A and at least one compound B are applied to said medium, these compounds being as defined in claim 1, and the combination of these compounds being in a total effective and non-phytotoxic amount 7. A method of combating, for curative or preventive purposes, against phytopathogenic fungi of cultures and / or against bacteria, characterized in that applies to the aerial parts of plants an effective and non-phytotoxic amount of a fungicidal and / or bactericidal composition according to any one of claims 1 to 5. 8. Control method according to claim 7 characterized in that a liquid is sprayed comprising the fungicidal and / or bactericidal composition according to any one of claims 1 to 5 on the aerial parts of the crops to be treated 9. A method of combating phytopathogenic fungi in crops and / or against bacteria according to claim 8, characterized in that a total dose of composition of between 1000 and 10000 g / ha is applied by foliar treatment, preferably between 1500 and 6000 g / ha. 10. Control method according to claim 9 characterized in that a total dose of composition is applied between 1800 and 2700 g / ha, and more advantageously a dose of 2025 g / ha. 11. A product comprising at least one compound A and at least one compound B for the control of phytopathogenic fungi and / or bacteria of a medium by simultaneous, sequential or separate application.