WO2008155416A2

WO2008155416A2 - Gibberellins as safeners for fungicides with phytotoxic activity

Info

Publication number: WO2008155416A2
Application number: PCT/EP2008/057892
Authority: WO
Inventors: Thomas J. Holt; Hendrik Leonard Ypema
Original assignee: Basf Se
Priority date: 2007-06-20
Filing date: 2008-06-20
Publication date: 2008-12-24
Also published as: WO2008155416A3

Abstract

The present invention relates to the use of at least one gibberellin for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with these fungicides. The invention also relates to a method for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with these fungicides by treating the seeds or the growing medium of the seeds also with at least one gibberellin. A further aspect of the invention is a method for controlling phytopathogenic fungi which comprises treating the seeds of a plant or the growing medium of the seeds with at least one azole fungicide in combination with at least one gibberellin and optionally at least one anilide fungicide. Finally, the invention relates to a composition comprising at least one azole fungicide, at least one gibberellin and optionally at least one anilide fungicide.

Description

Gibberellins as safeners for fungicides with phytotoxic activity

Description

The present invention relates to the use of at least one gibberellin for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with these fungicides. The invention also relates to a method for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with these fungicides by treating the seeds or the growing medium of the seeds also with at least one gibberellin. A further aspect of the invention is a method for controlling phytopathogenic fungi which comprises treating the seeds of a plant or the growing medium of the seeds with at least one azole fungicide in combi- nation with at least one gibberellin and optionally at least one anilide fungicide. Finally, the invention relates to a composition comprising at least one azole fungicide, at least one gibberellin and optionally at least one anilide fungicide.

It is known that some plant protecting agents may have a phytotoxic effect on crop plants treated therewith. For example, F. Montfort et al., Pesticide Science 46(4), 1996, 315-322, report that the use of azole fungicides, such as triticonazole, for the treatment of seed and crop plants may have an adverse effect on plant growth. For example, a greatly reduced longitudinal growth is observed when certain crop plants are treated with fluquinconazole or triticonazole.

Experiments carried out by the inventors of the present application have demonstrated that other phytotoxic effects, too, occur in plants which have been treated with azole fungicides or with a combination of azole fungicides and anilide fungicides, for example reduced or delayed germination, diminished emergence or a generally reduced plant vigor.

These disadvantageous effects, which are accompanied by yield losses and which, to some extent, ruin the fungicidal activity of these compounds, limit the economical benefit of using the fungicide.

WO 2007/065843 describes the use of a gibberellin as safener for azole fungicides. Explicitely, only the use of gibberellic acid and only for the purpose of reversing the stunting effect and the delayed or impeded germination of azole fungicides is disclosed.

Experiments carried out by the inventors of the present application have shown that the use of gibberellic acid, while being effective in considerably reverting the stunting effect and the delayed or impeded germination of azole fungicides, in some cases can lead to undesired side effects, such as a considerable stand loss (i.e. less plants in a determined area, mostly measured in a plant row, survive for a determined period after sowing).

It was furthermore observed that the combined use of azole fungicides with anilide fungicides, which is an effective combination for combating phytopathogenic fungi and especially soybean rust, in some cases has even stronger phytotoxic effects than the use of azole fungicides alone.

It is therefore an object of the present invention to provide compounds with a safening effect, i.e. compounds which reduce or prevent the negative effects of phytotoxically active fungicides, in particular of azole fungicides or of azole fungicides used in combination with anilide fungicides. The safening effect should not be limited to reversing the phytotoxic effects of azole fungicides used alone, but also of azole fungicides used in combination with anilide fungicides. Additionally or alternatively the safeners should show less side effects than the safeners of the prior art.

Surprisingly, it has been found that gibberellins prevent, or at least reduce, the phyto- toxic effects of such fungicides.

Accordingly, in a first aspect, the invention relates to a method for controlling phytopathogenic fungi which comprises treating the seeds of a plant or the growing medium of the seeds with at least one azole fungicide in combination with at least one gibberellin and optionally at least one anilide fungicide.

In a second aspect, the invention relates to a method for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and optionally with at least one anilide fungicide, which method comprises treating the seeds or the growing medium of the seeds with at least one azole fungicide and optionally at least one anilide fungicide in combination with at least one gibberellin.

In a third aspect, the invention relates to the use of at least one gibberellin for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and optionally at least one anilide fungicide.

In a fourth aspect, the invention relates to a composition comprising at least one azole fungicide, at least one gibberellin and optionally at least one anilide fungicide. Generally, the term "safener" is used for substances which reduce or prevent the damage to crop plants as the result of herbicides which are employed for destroying weeds. For the purposes of the present invention, however, this term is defined in more gen- eral terms and refers to substances which reduce or prevent the phytotoxic effect of crop protectants, in the present context specifically fungicides, on plants whose seeds or growth medium have been treated or are treated therewith. Thus, the subject matter of the present invention relates to the use of at least one gibberellin for reducing or preventing the phytotoxic effect of the above-named fungicides on plants whose seeds or whose growth substrates have been treated, or are treated, with these fungicides.

Naturally, the term "whose seeds" relates to the seed from which the plant has been grown and not the seed which it produces itself.

The term "seed" represents all types of plant propagation material. It comprises seeds in the actual sense, grains, fruits, tubers, the rhizome, spores, cuttings, slips, meristem tissue, individual plant cells and any form of plant tissue from which a complete plant can be grown. Preferably, it takes the form of seed in the actual sense.

"Growing medium", "growth medium" or "growth substrate" refers to any type of substrate in which the seed is sown and the plant grows or will grow, such as soil (for example in a pot, in borders or in the field) or artificial media. As a rule, it takes the form of the soil.

The remarks made below as to preferred embodiments of the fungicides, the gibberel- lins and other features of the invention are to be taken either alone or, preferably, in combination with each other.

The gibberellins are preferably selected among those of the formula I

in which

R represents a hydrogen atom or a hydroxyl group; and "^"" means that a single bond or a C-C double bond is present at this position.

The following four compounds of the formula 1-1 to I-4 come under the compounds of the formula I:

Gibberellin A₁ Gibberellin A₃ (gibberellic acid)

Gibberellin A, Gibberellin A₇

Gibberellins of the formula I and processes for their preparation are known and are described, for example, in WO 02/069715, hereby fully incorporated herein by reference.

The gibberellin is in particular selected from gibberellic acid (gibberellin A3) of the for- mula (I-2), gibberellin A₄ of the formula (I-3), gibberellin A7 of the formula (I-4) and a mixture thereof. More preferably the gibberellin is selected from gibberellin A₄ of the formula (I-3), gibberellin A₇ of the formula (I-4) and a mixture thereof. Even more preferably, the gibberellin is selected from a mixture of gibberellin A₄ of the formula (I-3) and gibberellin A₇ of the formula (I-4).

In case the at least one azole fungicide is used in combination with at least one anilide fungicide, the gibberellin is more preferably selected from gibberellin A₄ of the formula (I-3), gibberellin A₇ of the formula (I-4) and from a mixture thereof, and specifically from a mixture thereof. In some specific cases, the combined use of azole fungicides, anilide fungicides and gibberellins different from gibberellin A₄ and gibberellin A₇, in particular gibberellin A3, on the one side effectively reduces the phytotoxic activity of the fungicides, but, on the other side, in some cases may lead to secondary undesired effects caused by this specific combination, specifically to an enhanced stand loss. Under certain circumstances, especially when the plant is exposed to stress, and specifically to abiotic stress, such as drought or flood, the combined use of azole fungicides, anilide fungicides and gibberellin A3 may also lead to a decreased germination. For avoiding these undesired effects, it is preferred to use gibberellin A₄, gibberellin A₇ or more preferably a mixture thereof in these specific combinations. If a mixture of gibberellin A₄ and gibberellin A₇ is used, the two gibberellins are preferably present in a weight ratio of 20:1 to 1 :20, more preferably 10:1 to 1 :10, even more preferably 5:1 to 1 :5, in particular 2:1 to 1 :2 and specifically about 1 :1.

Azole fungicides, also referred to as conazole fungicides, are fungicidally active compounds which comprise an aromatic 5-membered heterocycle containing at least one nitrogen atom as ring member. In particular, they comprise an imidazole ring ("imidazole conazoles") or a triazole ring ("triazole conazoles").

Azole fungicides and processes for their preparation are, in principle, known to the skilled worker and described, for example, in Farm Chemicals Handbook, Meister Publishing Company or in the Compendium of Pesticide Common Names, http://www.hclrss.demon.co.uk/, which are herewith incorporated by reference.

Preferred azole fungicides are those which are known by the common names biter- tanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, metcona- zole, myclobutanil, paclobutrazole, penconazole, prochloraz, propiconazole, prothio- conazole, tebuconazole, triadimefon, triadimenol, triflumizole and triticonazole.

Especially preferred azole fungicides are selected among difenoconazole, epoxiconazole, fluquinconazole, flutriafol, imazalil, metconazole, paclobutrazole, prochloraz, propiconazole, prothioconazole, tebuconazole, triadimenol and triticonazole. More preferred are the azole fungicides selected among epoxiconazole, fluquinconazole, flutria- fol, prothioconazole, tebuconazole and triticonazole and even more preferred among epoxiconazole, fluquinconazole and triticonazole. In particular, they are selected among fluquinconazole and triticonazole. Specifically, the azole fungicide is triticonazole.

Anilide fungicides are fungicidally active compounds which comprise an anilide group (= phenyl-N H-CO-) or a sulfanilide group (= phenyl-NH-SO2-).

Anilide fungicides and processes for their preparation are, in principle, known to the skilled worker and described, for example, in Farm Chemicals Handbook, Meister Pub- lishing Company or in the Compendium of Pesticide Common Names, http://www.hclrss.demon.co.uk/, which are herewith incorporated by reference.

Preferred anilide fungicides are those which are known by the common names benal- axyl, benalaxyl-M, boscalid, carboxin, fenhexamid, isotianil, metalaxyl, metalaxyl-M, metsulfovax, ofurace, oxadixyl, oxycarboxin, pyracarbolid, thifluzamide and tiadinil, benzanilide fungicides, such as benodanil, flutolanil, mebenil, mepronil, salicylanilide and tecloftalam, furanilides, such as fenfuram, furalaxyl, furcarbanil and methfuroxam, and sulfanilides, such as flusulfamide. More preferred anilide fungicides are selected from benalaxyl, benalaxyl-M, boscalid, carboxin, fenhexamid, isotianil, metalaxyl, metalaxyl-M, metsulfovax, ofurace, oxadixyl, oxycarboxin, pyracarbolid, thifluzamide and tiadinil. Particularly preferred are metalaxyl and metalaxyl-M, metalaxyl being the unresolved isomeric mixture of the R and S enantiomers and metalaxyl-M, which is also known as mefenoxam, being the R enantiomer. Even more preferably, metalaxyl- M (mefenoxam) is used as anilide fungicide.

The above-described fungicides and gibberellins can also be employed in the form of their agriculturally tolerated salts. Thus, all compounds which comprise basic nitrogen atoms in the molecule (as is the case for example with all azole fungicides) can be employed in the form of their acid addition salts. Compounds with abstractable protons (for example with carboxyl groups, such as the gibberellin I) can be employed in the form of their salts with metal cations, ammonium ions, phosphonium ions, sulfonium ions or sulfoxonium ions.

The acid addition salts can be prepared for example by reaction of the free bases with a suitable Bronsted acid. Suitable acids have agriculturally tolerated acid anions and are selected for example among hydrohalic acids such as hydrofluoric acid, hydrochlo- ric acid, hydrobromic acid, and hydriodic acid, sulfuric acid, phosphoric acid, nitric acid, benzoic acid and Ci-C4-alkanoic acids such as formic acid, acetic acid, propionic acid and butyric acid.

Examples of suitable cations are, in particular, the cations of the alkali metals, prefera- bly lithium, sodium or potassium, of the alkaline earth metals, preferably calcium, magnesium or barium, and of the transition metals, preferably manganese, copper, zinc or iron. Suitable ammonium cations are the ammonium cation itself (NH₄ ⁺) and also substituted ammonium ions in which 1 to 4 of the hydrogen atoms are replaced by C1-C4- alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4- alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of suitable ammonium ions comprise methylammonium, ethylammonium, propylammonium, isopropylammonium, butylam- monium, dimethylammonium, diethylammonium, dipropylammonium, diisopropylam- monium, dibutylammonium, trimethylammonium, triethylammonium, tripropylammo- nium, tributylammonium, tetramethylammonium, tetraethylammonium, tetrapropylam- monium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium. Also suitable are phosphonium ions, sulfonium ions such as tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, such as tri(Ci-C4.alkyl)sulfoxonium.

Ci-C4-Alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Ci-C4-Hydroxyalkyl represents a Ci-C4-alkyl radical in which at least one hydrogen atom is replaced by a hydroxyl group. Examples are hydroxym ethyl, 1- and 2- hydroxyethyl, 1 ,2-dihydroxyethyl, 1-, 2- and 3-hydroxypropyl, 1 ,2-dihydroxypropyl, 1 ,3- dihydroxypropyl, 2,3-dihydroxypropyl, 1 ,2,3-trihydroxypropyl, 1-, 2-, 3- and 4-hydroxybutyl and the like.

Ci-C₄-AIkOXy represents a Ci-C4-alkyl radical which is bonded via an oxygen atom. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy.

Ci-C4-Alkoxy-Ci-C4-alkyl represents a Ci-C4-alkyl radical in which at least one hydrogen atom is replaced by an alkoxy group. Examples are methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, isobutoxymethyl, tert-butoxymethyl, methoxyethyl, 1- and 2-ethoxyethyl, 1- and 2-propoxyethyl, 1- and 2- isopropoxyethyl, 1- and 2-butoxyethyl, 1- and 2-sec-butoxyethyl, 1- and 2- isobutoxyethyl, 1- and 2-tert-butoxyethyl, 1-, 2- and 3-methoxypropyl, 1-, 2- and 3- ethoxypropyl, 1-, 2- and 3-propoxypropyl, 1-, 2- and 3-isopropoxypropyl, 1-, 2- and 3- butoxypropyl, 1-, 2- and 3-sec-butoxypropyl, 1-, 2- and 3-isobutoxypropyl, 1-, 2- and 3- tert-butoxypropyl and the like.

Hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl represents a Ci-C4-alkyl radical, in which at least one hydrogen atom is replaced by at least one alkoxy group. In addition, at least one hydrogen atom in the alkyl radical or in the alkoxy radical or in both is replaced by a hydroxyl group. Examples are (2-hydroxyethoxy)methyl, (2- und 3-hydroxypropoxy)- methyl, (2-hydroxyethoxy)ethyl, (2- and 3-hydroxypropoxy)-1 -ethyl, (2- and 3-hydroxy- propoxy)-2-ethyl, 2-ethoxy-1-hydroxyethyl and the like.

Gibberellins which comprise a carboxyl group in the molecule, such as, for example, the gibberellins of the formula I, may be employed not only in the form of their salts, but also in ester form. Suitable esters are in particular those with Ci-C4-alkanols such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert- butanol.

The use according to the invention of gibberellins as safeners reduces or prevents the phytotoxic effect which certain azole fungicides or combinations of azole fungicides and anilide fungicides exert on the seeds treated therewith or on plants which are grown from seeds treated therewith or which grow in a growth substrate treated therewith.

The phytotoxic effect which these fungicides have can manifest itself in various ways and can be recognized by comparing plants whose seeds and/or whose growth substrate have been treated with a phytotoxically active fungicide and plants whose seeds and/or whose growth substrate have not been treated with this fungicide. Naturally, the comparison must be carried out under pathogen-free conditions since otherwise the untreated plants might, as the result of infection, display symptoms which correspond to the phytotoxic effects or are similar thereto.

The phytotoxic effect manifests itself for example in that seeds which have been treated with the fungicide in question and/or which are sown in a fungicide-treated growth substrate germinate more poorly. Poorer germination means that the same number of seeds gives rise to fewer seedlings in comparison with seeds which have not been treated with the fungicide in question and which grow in a correspondingly untreated growth substrate.

Alternatively, or additionally, the phytotoxic effect may manifest itself in reduced emergence. "Emergence" is understood as meaning that the seedling appears from the soil (or, in other words, that the coleoptil or the cotyledons or the shoot or the leaf break through the soil surface). Reduced emergence means that fewer seedlings appear from the soil from the same number of seeds in comparison with seeds which have not been treated with the fungicide in question and which germinate and grow in a growth substrate which has not been treated correspondingly.

In some plant species, germination and emergence may coincide, i.e. the first cotyledon already appears from the soil. However, since this is not the case with all plants, germination and emergence are described separately.

Alternatively or in addition, the phytotoxic effect can manifest itself in reduced growth of the hypocotyl, i.e. the stalk does not grow as long as expected, and, possibly, leaves and apex lie on the ground. In terms of the present invention, this effect is also called "stunting effect". In some plants, such as cereals, this characteristic is not necessarily disadvantageous since it reduces or prevents lodging; in some plant species, however, such as legumes, it is entirely undesirable.

Globally, the phytotoxic effect of the fungicide may manifest itself in diminished vitality of the plants (= plant vigor). Diminished vitality can be ascertained by comparison with plants whose seeds and/or whose growth substrate have not been treated with the phytotoxic fungicide in question. The vitality of a plant manifests itself in a variety of factors. Examples of factors which are manifestations of the plant's vitality are:

(a) overall visual appearance;

(b) root growth and/or root development;

(c) size of the leaf area; (d) intensity of the leaves' green coloration;

(e) number of dead leaves in the vicinity of the ground;

(f) plant height; (g) plant weight; (h) growth rate;

(i) appearance and/or number of fruits; (j) plant stand density; (k) germination behavior;

(I) emergence behavior; (m) shoot number; (n) shoot type (quality and productivity)

(0) toughness of the plant, for example resistance to biotic or abiotic stress; (p) presence of necroses;

(q) senescence behavior.

Accordingly, the phytotoxic effect can manifest itself in a worsening of at least one of the abovementioned factors, for example in

(a) a poorer overall visual appearance;

(b) poorer root growth and/or poorer root development;

(c) reduced size of the leaf area;

(d) less intense green coloration of the leaves; (e) more dead leaves in the vicinity of the ground;

(f) lower plant height ("stunting" of the plant, see also hereinabove);

(g) lower plant weight; (h) poorer growth rate;

(1) poorer appearance and/or lower number of fruits; (j) lower plant stand density;

(k) poorer germination behavior (see hereinabove); (I) poorer emergence behavior (see hereinabove); (m) fewer shoots;

(n) shoots in lower quality (for example weak shoots), less productive shoots (o) reduced toughness of the plant, for example reduced resistance to biotic or abiotic stress; (p) presence of necroses; (q) poorer senescence behavior (earlier senescence).

Biotic stress is caused by organisms, for example by pests (such as insects, arachnids, nematodes and the like), competing plants (for example weeds), phytopathogenic fungi and other microorganisms such as bacteria and viruses. Abiotic stress is triggered for example by extreme temperatures such as heat, chill, great variations in temperature, or unseasonal temperatures, drought, extreme wetness, high salinity, radiation (for example increased UV radiation as the result of the diminishing ozone layer), increased amount of ozone in the vicinity of the soil and/or organic and inorganic pollution (for example as the result of phytotoxic amounts of pesticides or contamination with heavy metals). Biotic and abiotic stress leads to a reduced quantity and/or quality of the stressed plant and its fruits. Thus, for example, the synthesis and accumulation of proteins is mainly adversely affected by temperature stress, while growth and polysaccharide synthesis are reduced by virtually all stress factors. This leads to biomass losses and to a reduced nutrient content of the plant product.

In a preferred embodiment, the invention relates to the use of the above-described gib- berellins for improving the vitality of plants whose seeds and/or whose growth medium have been treated, or are treated, with at least one azole fungicide and optionally also with at least one anilide fungicide as defined hereinabove.

In one preferred embodiment, the improved plant vigor manifests itself in an improved germination. Accordingly, in a more preferred embodiment, the invention relates to the use of the above-described gibberellins for improving the germination of plants whose seeds and/or growth medium have been treated, or are treated, with at least one azole fungicide and optionally also with at least one anilide fungicide as defined hereinabove. Improved germination means that the same number of seeds gives rise to more seedlings in comparison with seeds which have been treated with the fungicide in question and/or which grow in a correspondingly treated growth substrate, but which have not been treated with a gibberellin or the growing medium of which has not been treated with a gibberellin.

In another preferred embodiment, the improved plant vigor - additionally or alternatively

- manifests itself in an improved emergence. Accordingly, in a more preferred embodi- ment, the invention relates to the use of the above-described gibberellins for improving the emergence of plants whose seeds and/or whose growth medium have been treated, or are treated, with at least one azole fungicide and optionally also with at least one anilide fungicide as defined hereinabove. Improved emergence means that more seedlings appear from the soil from the same number of seeds in comparison with seeds which have been treated with the fungicide in question and/or which germinate and grow in a growth substrate which has been treated correspondingly, but which have not been treated with a gibberellin or the growing medium of which has not been treated with a gibberellin.

- manifests itself in a reduced stunting, or, in other words, in an increased plant height. Accordingly, in a more preferred embodiment, the invention relates to the use of the above-described gibberellins for reducing or preventing the stunting effect of azole fungicides or of combinations of azole fungicides with anilide fungicides on plants whose seeds and/or whose growth medium have been treated, or are treated, with at least one azole fungicide and optionally also with at least one anilide fungicide as defined hereinabove, and thus for increasing the plant height of these plants. Reduced/pre- vented stunting or increased plant height means that the hypocotyl, i.e. the stalk, is at the same point of time higher than the stalk of plants whose seeds or whose growth medium have been treated with the fungicide in question, but which have not been treated with a gibberellin or the growing medium of which has not been treated with a gibberellin.

In particular, the invention relates to the use of at least one of the above-mentioned gibberellins for improving the plant vigor, in particular for improving the germination and/or the emergence and/or for reducing/preventing the stunting, of plants whose seeds have been treated with a fungicide as defined hereinabove.

In principle, the plants can take the form of all plant species and plant varieties which are usually treated with the above-described fungicides and where a phytotoxic effect is observed as the result of this treatment. As a rule, these plants are agriculturally use- ful plants or else ornamentals. Agriculturally useful plants are crop plants where parts or the entire plant act as a raw material for foodstuffs, feeding stuffs, fibers (for example cotton, linen), fuels (for example timber, bioethanol, biodiesel, biomass) or other chemical compounds. Examples are cereals such as wheat (inclusive spelt, einkorn, emmer, kamut, durum and triticale), rye, barley, oats, rice, wild rice, maize (corn), mil- let, sorghum and teff, pseudocereals such as amaranth, quinoa and buckwheat, legumes of agricultural use such as bean, vegetable pea, fodder pea, chickpea, lentil, soybean and peanut, oilseed rape, sunflower, cotton, sugar beet, stone fruit, pome fruit, citrus fruit, banana, strawberry, blueberry, almond, grape, mango, pawpaw, potato, tomato, capsicum (pepper), cucumber, pumpkin/squash, melon, watermelon, gar- lie, onion, carrot, cabbage, lucerne, clover, flax, elephant grass (Miscanthus), grass, lettuce, sugar cane, tea, tobacco and coffee.

Preferred agriculturally useful plants are selected from the above cereals, legumes, sunflower and sugar cane, more preferably from soybean, maize, wheat, triticale, oats, rye, barley, oilseed rape, millet, sorghum, rice, sunflower and sugar cane, and even more preferably from soybean, wheat, maize and oilseed rape. In particular, the plant is soybean.

Alternatively, preferred agriculturally useful plants are selected among potato, tomato, capsicum (pepper), cucumber, pumpkin/squash, melon, watermelon, garlic, onion, carrot, cabbage, bean, vegetable pea, fodder pea and lettuce, more preferably among tomato, onion, lettuce and pea.

Examples of ornamentals are turf, geranium, pelargonium, petunia, begonia and fuch- sia, to mention only a few examples of a large number of ornamentals.

The plants can be non-transgenic or transgenic in nature. In one embodiment of the invention, if the plant is transgenic, it is preferred that the recombinant modification of the transgenic plant is such in nature that the plant has resistance to a certain pesticide. For example, the transgenic plant can have a resis- tance to the herbicide glyphosate. Examples of transgenic plants are those with a resistance to herbicides from the group of the sulfonylurea (see, for example, EP-A- 0257993, US 5,013,659), the imidazolinones (see, for example, US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), of the glyfosinate type (see, for example, EP-A-0242236, EP-A-242246) or of the glyphosate type (see, for example, WO 92/00377) or plants with resistance to herbicides from the group of the cyclohexadienones/aryloxyphenoxypropionic acid herbicides (see, for example, US 5,162,602, US 5,290,696, US 5,498,544, US 5,428,001 , US 6,069,298, US 6,268,550, US 6,146,867, US 6,222,099, US 6,414,222) or transgenic plants such as cotton which are capable of forming Bacillus thuringiensis toxins (Bt toxins) which may make them resistant to certain pests (see, for example, EP-A-0142924, EP-A- 0193259). A preferred transgenic plant is a transgenic soybean plant, preferably having a transgenic event that confers resistance to a pesticide, preferably for the herbicide glyphosate. Accordingly, it is preferred that the transgenic soybean plant be one having a transgenic event that provides glyphosate resistance. More preferably, the transgenic soybean plant has the characteristics of "Roundup-Ready" transgenic soybeans (available from Monsanto Company, St. Louis, Mo.).

It is to be understood, however, that when the plant is a transgenic plant, the trans- genie events that are present in the plant are by no means limited to those that provide pesticide resistance, but can include any transgenic event. In fact, the use of "stacked" transgenic events in a plant is also contemplated.

As regards the manner and the amount in which the above-described fungicides and gibberellins are employed, reference is made to what is said hereinbelow in connection with the method according to the invention.

The present invention furthermore relates to a method of reducing or preventing the phytotoxic effect of azole fungicides or of azole fuingicides used in combination with anilide fungicides on plants whose seeds and/or whose growth substrates have been or are treated with these fungicides, where the plant' seed and/or its growth substrate is treated with at least one azole fungicide or with at least one azole fungicide and at least one anilide fungicide in combination with at least one of the above-described gibberellins.

As regards suitable and preferred fungicides, gibberellins and plants, reference is made to what has been said above. The method is preferably used for reducing or preventing the phytotoxic effect of azole fungicides or of azole fuingicides used in combination with anilide fungicides on plants, whose seeds have been treated with at least one azole fungicide or with at least one azole fungicide and at least one anilide fungicide, where the seeds of the plant are treated with at least one azole fungicide or with at least one azole fungicide and at least one anilide fungicide in combination with at least one of the above-described gibberel- lins.

The method is preferably used for improving the germination and/or the emergence and/or the vitality, more preferably for improving the germination and/or the emergence and/or reducing/preventing the stunting of the plant treated thus.

The treatment of the plants' seed and/or its growth substrate can be accomplished for example in such a way that the seed and/or the growth substrate is treated with a mixture of the at least one azole fungicide, the at least one gibberellin and optionally the at least one anilide fungicide. Alternatively, the seed and/or the growth substrate can be treated with the at least one azole fungicide, the at least one gibberellin and optionally the at least one anilide fungicide in separate form, it being possible for the treatment with the individual active substances to be accomplished simultaneously or in succession. In the case of successive treatment, the time interval may be from a few seconds up to several months, for example up to 6, 8 or even 10 months. However, the time interval must be such that the desired effect can take place. Preferably, the interval between the treatments is relatively short, i.e. fungicide(s) and gibberellin are applied within a time interval of from a few seconds up to at most one month, especially preferably up to not more than one week and in particular up to not more than one day. In principle, it is possible to apply the different active substances to different subjects (subjects being, in the present context, seed and growth substrate), that is, for example, to treat the seed with one of the active substances, for example with the fungi- cide(s), and to apply the other active substance(s), for example the gibberellin, to the growth substrate therewith. However, it is preferred to apply all active substances to the same subject. In the case of the successive treatment, the sequence in which the individual active substances are applied is, as a rule, not critical.

If the growth medium is treated according to the invention, this treatment preferably takes place before emergence of the plant.

It is especially preferred to treat the seed. Here, the seed may be treated before sowing or else via the growth substrate into which it is sown, for example during sowing in the form of what is known as the in-furrow application. In this form of application, the plant protectant is placed into the furrow essentially at the same time as the seed. Preferably, the seed is treated before sowing. In principle, all customary methods of treating and in particular dressing such as coating (e.g. pelleting) and imbibing (e.g. soaking) seeds can be employed. Specifically, the seed treatment follows a procedure in which the seed is exposed to the specifically desired amount of a preparation com- prising the active compounds used according to the invention (= at least one azole fungicide, at least one gibberellin and optionally at least one anilide fungicide). The preparation may be a formulation that is applied as such or after previously diluting it, e.g. with water; for instance, it may be expedient to dilute seed treatment formulations 2-10 fold leading to concentrations in the ready-to-use compositions of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.

Usually, a device which is suitable for this purpose, for example a mixer for solid or solid/liquid components, is employed until the preparation is distributed uniformly on the seed. Thus, the preparation can be applied to seeds by any standard seed treat- ment methodology, including but not limited to mixing in a container (e.g., a bottle, bag or tumbler), mechanical application, tumbling, spraying, and immersion. If appropriate, this is followed by drying.

Particular embodiments of the present invention comprise seed coating and imbibition (e.g. soaking). "Coating" denotes any process that endows the outer surfaces of the seeds partially or completely with a layer or layers of non-plant material, and "imbibition" any process that results in penetration of the active ingredient(s) into the ger- minable parts of the seed and/or its natural sheath, (inner) husk, hull, shell, pod and/or integument. The invention therefore also relates to a treatment of seeds which com- prises providing seeds with a coating that comprises the active compounds used according to the invention, and to a treatment of seeds which comprises imbibition of seeds with the active compounds used according to the invention.

Coating is particularly effective in accommodating high loads of the active compounds, as may be required to treat typically refractory fungal pathogens, while at the same time excessive phytotoxicity is avoided.

Coating may be applied to the seeds using conventional coating techniques and machines, such as fluidized bed techniques, the roller mill method, rotostatic seed treat- ers, and drum coaters. Other methods such as the spouted beds technique may also be useful. The seeds may be pre-sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing.

Such procedures are known in the art. Seed coating methods and apparatus for their application are disclosed in, for example, US 5,918,413, US 5,891 ,246, US 5,554,445, US 5,389,399, US 5,107,787, US 5,080,925, US 4,759,945 and US 4,465,017. In another particular embodiment, the active compounds used according to the invention can be mixed directly with seeds, for instance as a solid fine particulate formulation, e.g. a powder or dust. Optionally, a sticking agent can be used to support the adhesion of the solid, e.g. the powder, to the seed surface. For example, a quantity of seed can be mixed with a sticking agent (which increases adhesion of the particles on the surface of the seed) and optionally agitated to encourage uniform coating of the seed with the sticking agent. For example, the seed can be mixed with a sufficient amount of sticking agent, which leads to a partial or complete coating of the seed with sticking agent. The seed pretreated in this way is then mixed with a solid formulation containing the active compounds used according to the invention to achieve adhesion of the solid formulation on the surface of the seed material. The mixture can be agitated, for example by tumbling, to encourage contact of the sticking agent with the solid formulation of active compounds used according to the invention, thereby causing the active compounds used according to the invention to stick to the seed.

Another particular method of treating seed with the active compounds used according to the invention is imbibition. For example, seed can be combined for a period of time with an aqueous solution comprising from about 1 % by weight to about 75% by weight of the active compounds in a solvent such as water. Preferably the concentration of the solution is from about 5% by weight to about 50% by weight, more preferably from about 10% by weight to about 25% by weight. During the period in which the seed is combined with the solution, the seed takes up (imbibes) at least a portion of the active compounds. Optionally, the mixture of seed and solution can be agitated, for example by shaking, rolling, tumbling, or other means. After the imbibition process, the seed can be separated from the solution and optionally dried in a suitable manner, for example by patting or air-drying.

In yet another particular embodiment of the present invention, the active compounds used according to the invention can be introduced onto or into a seed by use of solid matrix priming. For example, a quantity of the active compounds can be mixed with a solid matrix material, and then the seed can be placed into contact with the solid matrix material for a period to allow the active compounds to be introduced to the seed. The seed can then optionally be separated from the solid matrix material and stored or used, or, preferably, the mixture of solid matrix material plus seed can be stored or planted/sown directly.

The ratio of the total weight of fungicide(s) employed according to the invention to the total weight of gibberellin(s) employed in accordance with the invention is preferably 200:1 to 1 :1 , e.g. 200:1 to 2:1 or 200:1 to 4:1 , more preferably 100:1 to 1 :1 , e.g. 100:1 to 2:1 or 100:1 to 4:1 , even more preferably 50:1 to 1 :1 , e.g. 50:1 to 2:1 or 50:1 to 4:1 , and specifically 30:1 to 1 :1 , e.g. 30:1 to 2:1 or 30:1 to 4:1. If at least one anilide fungicide is used, then the ratio of the total weight of azole fungicide^) employed in accordance with the invention to the total weight of anilide fungicide^) employed in accordance with the invention is preferably 100:1 to 1 :1 , e.g. 100:1 to 2:1 , more preferably 50:1 to 1 :1 , e.g. 50:1 to 2:1 , and even more preferably 30:1 to 1 :1 , e.g. 30:1 to 2:1.

If two different gibberellins are used, their weight ratio is preferably 20:1 to 1 :20, more preferably 10:1 to 1 :10, even more preferably 5:1 to 1 :5, in particular 2:1 to 1 :2 and specifically about 1 :1.

The active substances (i.e. the at least one azole fungicide, the at least one gibberellin and the at least one optionally employed anilide fungicide) can be formulated, in the ready-to-use preparations, in suspended, emulsified or dissolved form, either jointly or separately. The use forms depend entirely on the intended purposes.

The active substances can be employed as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, tracking powders or granules. The application is usually accomplished by spraying, misting, atomizing, scattering or pouring. The use forms and use methods depend on the intended purposes; in any case, they should ensure the finest possible distribution of the active substances.

Depending on the presentation in which the ready-to-use preparations of the active substances are present, they comprise one or more liquid or solid carriers, optionally surface-active substances and optionally further adjuvants which are conventionally used for the formulation of plant protectants. The compositions for such formulations are well known to the skilled worker.

Aqueous use forms can be prepared for example starting from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the active substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, adhesive, dispersant or emulsifier. However, it is also possible to prepare concentrates consisting of active substance, wetter, adhesive, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The concentrations of the active substances in the ready-to-use preparations can be varied within substantial ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1 % (% by weight total active substance content based on the total weight of the ready-to-use preparation). The active substances can also be employed successfully in the ultra-low-volume method (ULV), it being possible to apply formulations with more than 95% by weight of active substance, or indeed the active substances without additives.

It is possible to add, to the active substances, oils of various types, wetters, adjuvants, herbicides, fungicides which are other than the fungicides employed in accordance with the invention, insecticides, nematicides, other pesticides such as bactericides, algi- cides, molluscicides, rodenticides, and bird/mammal repellents, safeners, fertilizers and/or growth regulators which are other than the gibberellins employed in accordance with the invention, if appropriate only just before use (tank mix). These can be admixed to the active substances employed in accordance with the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.

Adjuvants within this meaning are, in particular, organic modified polysiloxanes, for example Break Thru S 240^®; alcohol alkoxylates, for example Atplus 245^®, Atplus MBA 1303^®, Plurafac LF 300^® and Lutensol ON 30^®; EO/PO block polymers, for example Pluronic RPE 2035^® and Genapol B^®; alcohol ethoxylates, for example Lutensol XP 80^®; and sodium dioctyl sulfosuccinate, for example Leophen RA^®.

To widen the spectrum of action, the active ingredients can also be employed together with other active ingredients which are useful in seed treatment, for example together with fungicides, insecticides, molluscicides, nematicides, herbicides, algicides, bactericides, rodenticides, bird/mammal repellents, growth regulators, safeners or also fertiliz- ers.

The following list of active ingredients with which the active ingredients can be used in accordance with the invention is intended to illustrate the possible combinations, but not to impose any limitation:

• Fungicides:

(1.1 ) amine derivatives such as guazatine;

(1.2) anilinopyrimidines such as pyrimethanil, mepanipyrim and cyprodinil;

(1.3) dicarboximides such as iprodione, procymidone, vinclozolin; (1.4) dithiocarbamates such as mancozeb, metiram and thiram;

(1.5) heterocylic compounds such as benomyl, carbendazim, fuberidazole, picobenzamid, penthiopyrad, proquinazid, thiabendazole and thiophanate- methyl;

(1.6) phenylpyrroles such as fenpiclonil and fludioxonil; (1.7) other fungicides, for example benthiavalicarb, cyflufenamid, fosetyl, fosetyl- aluminium, phosphorous acid and its salts, iprovalicarb and metafenone; (1.8) strobilurins such as azoxystrobin, dimoxystrobin, enestrobin, enestroburin, fluox- astrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclo- strobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)- ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6-methylpyridin-2-ylmethoxy- imino)ethyl]benzyl)carbamate and methyl 2-ortho-[(2,5-dimethylphenyloxy- methylene)phenyl]-3-methoxyacrylate;

(1.9) cinnamides and analogous compounds such as dimethomorph, flumetover and flumorph;

• Insecticides/acaricides:

(2.1 ) organo(thio)phosphates selected from acephate, azamethiphos, azinphos- methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosa- lone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos and trichlorfon;

(2.2) carbamates selected from alanycarb, aldicarb, bendiocarb, benfuracarb, car- baryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb and triazamate;

(2.3) pyrethroids selected from allethrin, bifenthrin, cycloprothrin, cyfluthrin, cy- halothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fen- valerate, flucythrinate, imiprothrin, lambda-cyhalothrin, gamma-cyhalothrin, per- methrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, te- fluthrin, tetramethrin, tralomethrin, transfluthrin and profluthrin, dimefluthrin;

(2.4) growth regulators selected from a) chitin synthesis inhibitors that are selected from the benzoylureas bistrifluron, chlorfluazuron, cyramazin, diflubenzuron, flu- cycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole and clofentazine; b) ecdysone antagonists that are selceted from halofenozide, methoxyfenozide, te- bufenozide and azadirachtin; c) juvenoids that are selected from pyriproxyfen, methoprene and fenoxycarb and d) lipid biosynthesis inhibitors that are selected from spirodiclofen, spiromesifen and spirotetramat; (2.5) nicotinic receptor agonist/antagonist compounds selected from clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid;

(2.6) GABA antagonist compounds selected from acetoprole, endosulfan, ethiprole, fipronil, vaniliprole,

(2.7) macrocyclic lactone insecticides selected from abamectin, emamectin, milbe- mectin, lepimectin and spirosad;

(2.8) METI I compounds selected from fenazaquin, pyridaben, tebufenpyrad, tolfen- pyrad and flufenerim; (2.9) METI Il and III compounds selected from acequinocyl, fluacyprim and hydrame- thylnon; (2.10) uncoupler compounds: chlorfenapyr;

(2.11 ) oxidative phosphorylation inhibitor compounds selected from cyhexatin, diafen- thiuron, fenbutatin oxide and propargite;

(2.12) moulting disruptor compounds: cyromazine;

(2.13) mixed function oxidaes inhibitor compounds: piperonyl butoxide;

(2.14)sodium channel blocker compounds selected from metaflumizone and indox- acarb; (2.15)a compound selected from benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, cyenopyrafen, flupyrazofos, cy- flumetofen, amidoflumet, the aminoisothiazole compound of formula r¹

wherein R¹ is -CH₂OCH₂CH₃ or H and R" is CF₂CF₂CF₃ or CH₂C(CHs)₃; anthranilamide compounds of formula F²

wherein B¹ is hydrogen, CN or Cl, B² is Br or CF₃, and R^B is hydrogen, CH₃ or

CH(CH₃)₂; and malonitrile compounds as described in JP 2002-284608, WO 02/89579, WO 02/90320, WO 02/90321 , WO 04/06677, WO 04/20399 or JP 2004-99597.

• Molluscicides;

• Nematicides;

• Herbicides, for example imidazolinone herbicides such as imazethapyr, imazamox, imazapyr and imazapic, or dimethenamid-p;

• Algicides; • Bactericides;

• Biologicals; • Bird / mammal repellents;

• Fertilizers;

• Fumigants;

• Growth regulators; • Rodenticides.

Molluscicides, nematicides, herbicides, algicides, bactericides, biologicals, bird / mammal repellents, fertilizers, fumigants, growth regulators and rodenticides are well known to a person skilled in the art.

Preferred insecticides are selected from acetamiprid, alpha-cypermethrin, beta- cypermethrin, bifenthrin, carbofuran, carbosulfan, clothianidin, cycloprothrin, cyfluthrin, cypermethrin, deltamethrin, diflubenzuron, dinotefuran, etofenprox, fenbutatin-oxide, fenpropathrin, fipronil, flucythrinate, imidacloprid, lambda-cyhalothrin, nitenpyram, pheromones, spinosad, teflubenzuron, tefluthrin, terbufos, thiacloprid, thiamethoxam, thiodicarb, tralomethrin, triazamate, zeta-cypermethrin, spirotetramat , flupyrazofos, tolfenpyrad, flubendiamide, bistrifluron, benclothiaz, pyrafluprole, pyriprole, amidoflu- met , flufenerim, cyflumetofen, cyenopyrafen, the anthranilamide compound of formula r² where B¹ is Cl, B² is Br and R^B is CH3, and the anthranilamide compound of formula r² where B¹ is CN, B² is Br and R^B is CH₃.

More preferred insecticides are GABA antagonist compounds, herein preferred being fipronil, and nicotinic receptor agonist/antagonist compounds, herein preferred being clothianidin, imidacloprid and thiamethoxam. A particularly preferred insecticide is fipronil.

In a specific embodiment of the invention, no further fungicides are employed in addition to the fungicides employed in accordance with the invention. In a more specific embodiment, no further active compounds except the at least one azole fungicide, the at least one gibberellin and the at least one optionally used anilide fungicide are employed in the method and the composition of the invention.

The formulations containing the active ingredients according to the invention are prepared in a known manner, e.g. by extending the active substances with solvents and/or carriers, if desired using surface-active substances, i.e. emulsifiers and dispersants. Solvents/auxiliaries which are suitable are essentially:

water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, methyl hydroxybutyl ketone, diacetone alcohol, mesityl oxide, isophorone), lactones (for example gamma-butyrolacton), pyrrolidones (pyrrolidone, N-methylpyrrolidone, N- ethylpyrrolidone, n-octylpyrrolidone), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

- carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

Surface active compounds are all those surfactants which are suitable for formulating agrochemical actives, in particular for the active ingredients used according to the present invention, and which may be nonionic, cationic, anionic or amphoteric. According to their action, surfactants - sometimes referred to as "additives" - may be divided into wetters, dispersants, emulsifiers or protective colloids; however, these particular groups may overlap and cannot be divided strictly.

Suitable wetters are all those substances which promote wetting and which are conventionally used for formulating agrochemical active ingredients. Alkylnaphthalenesul- fonates such as diisopropyl- or diisobutylnaphthalenesulfonat.es can be used preferably.

Dispersants and/or emulsifiers which are suitable are all nonionic, anionic and cationic dispersants or emulsifiers conventionally used for formulating agrochemical active in- gredients. The following can preferably be used: nonionic or anionic dispersants and/or emulsifiers or mixtures of nonionic or anionic dispersants and/or emulsifiers.

Suitable nonionic dispersants and/or emulsifiers which may be employed are, in particular, ethylene oxide/alkylene oxide block copolymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, for example polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, tristearyl phenyl polyglycol ether, alkylarylpolyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters and methyl cellulose.

Suitable anionic dispersants which and/or emulsifiers which may be employed are, in particular, alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alky- larylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore arylsulfonate/formaldehyde condensates, for example condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, ligninsulfonates, lignin-sulfite waste liquors, phosphated or sulfated derivatives of methylcellulose, and salts of polyacrylic acid.

Protective colloids are typically water soluble, amphiphilic polymers. Examples include proteins und denatured proteins such as casein, polysaccharides such as water soluble starch derivatives and cellulose derivatives, in particular hydrophobic modified starch and celluloses, furthermore polycarboxylates such as polyacrylic acid and acrylic acid copolymers, polyvinylalcohol, polyvinylpyrrolidone, vinylpyrrolidone copolymers, polyvi- nyl amines, polyethylene imines and polyalkylene ethers.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, mesityl oxide, isophorone, strongly polar solvents, for example dimethyl sulfoxide, 2-pyrrolidone, N- methylpyrrolidone, butyrolactone and water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

Formulations for the treatment of seed may additionally comprise binders and/or gelling agents and, if appropriate, colorants.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, in particular from 5 to 50% by weight, of the active substance. The active substances are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum). For the treatment of seed, the relevant formulations will, after having been diluted by a factor of two to ten, give active substance concentrations of from 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in the ready-to-use preparations.

The following are examples of formulations:

1. Products for dilution with water

I) Water-soluble concentrates (SL, LS) 10 parts by weight of active substance are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other adjuvants are added. The active substance dissolves upon dilution with water. This gives a formulation with an active substance content of 10% by weight.

II) Dispersible concentrates (DC)

20 parts by weight of active substance are dissolved in 70 parts by weight of cyclohex- anone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. The active substance content is 20% by weight. Dilution with water gives a dispersion.

III) Emulsifiable concentrate (EC)

15 parts by weight of active substance are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). The formulation has an active substance content of 15% by weight. Dilution with water gives an emulsion.

IV) Emulsions (EW, EO, ES)

25 parts by weight of active substance are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. The formulation has an active substance content of 25% by weight.

V) Suspensions (SC, OD, FS) In an agitated ball mill, 20 parts by weight of active substance are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. The active substance content in the formulation is 20% by weight. Dilution with water gives a stable suspension of the active substance.

VI) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of active substance are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). The formulation has an active substance content of 50% by weight. Dilution with water gives a stable dispersion or solution of the active substance.

VII) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)

75 parts by weight of active substance are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. The active substance content of the formulation is 75% by weight. Dilution with water gives a stable dispersion or solution of the active substance.

VIII) Gel formulations (GF)

In a ball mill, 20 parts by weight of active substance, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or of an organic solvent are mixed to give a fine suspension.

2. Products to be applied undiluted

IX) Dusts (DP, DS)

5 parts by weight of active substance are ground finely and mixed intimately with

95 parts by weight of finely divided kaolin. This gives a tracking powder with an active substance content of 5% by weight.

X) Granules (GR, FG, GG, MG)

0.5 parts by weight of active substance are ground finely and associated with 95.5 parts by weight of carriers. Current methods here are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted with an active substance content of 0.5% by weight.

Xl) ULV solutions (UL)

10 parts by weight of active substance are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted with an active substance content of 10% by weight.

Suitable formulations for the treatment of seeds are, for example:

I water-soluble concentrates (LS)

III emulsifiable concentrates (EC) IV emulsions (ES)

V suspensions (FS)

VI water-dispersible granules and water-soluble granules (SG) VII water-dispersible powders and water-soluble powders (WS, SS)

VIII gel formulations (GF)

IX dusts and dust-like powders (DS)

For the treatment of seed, powders, such as water-dispersible, water-soluble and dustable powders, dusts and suspensions are preferred. Further, gel formulations are preferred. Also, water-soluble concentrates and emulsions may be expediently used.

The following formulations are particularly preferred for seed treatment: flowable con- centrates (especially FS); solutions (especially LS); powders for dry treatment (especially DS); water dispersible powders for slurry treatment (especially WS); water- soluble powders (especially SS) and emulsions (especially ES). Also preferred are gel formulations (especially GF). These formulations can be applied to the seed diluted or undiluted.

It is even more preferred to use FS formulations. Usually, such formulations comprise from 1 to 800 g/l active substances, 1 to 200 g/l surfactants, 0 to 200 g/l antifreeze agent, 0 to 400 g/l binder, 0 to 200 g/l colorants and solvents, preferably water.

Preferred FS formulations of the active substances for the treatment of seed usually comprise 0.5 to 80% active substance, 0.05 to 5% wetter, 0.5 to 15% dispersant, 0.1 to 5% thickener, 5 to 20% antifreeze agent, 0.1 to 2% antifoam, 1 to 20% pigment and/or colorants, 0 to 15% adhesive or sticker, 0 to 75% filler/vehicle and 0.01 to 1 % preservative.

In general, a seed treatment formulation preferably comprises at least one auxiliary agent that is specifically suited for the seed treatment, i.e. an auxiliary agent which in particular promotes adhesion of the active ingredients to and/or penetration into the seeds and/or otherwise improves stability and/or manageability of the composition or the seeds treated therewith.

In particular, seed treatment auxiliary agents are selected from the group consisting of agents suitable for seed coating materials, agents suitable for solid matrix priming materials, penetration enhancers suitable for promoting seed imbibition, colorants, anti- freezes, and gelling agents.

According to a preferred embodiment, the seed coating material comprises a binder (or sticker). Optionally, the coating material also comprises one or more additional seed treatment auxiliary agents selected from the group consisting of fillers and plasticizers. Binders (or stickers) are all customary binders (or stickers) which can be employed in seed treatment formulations. Binders (or stickers) that are useful in the present invention preferably comprise an adhesive polymer that may be natural or partly or wholly synthetic and is without phytotoxic effect on the seed to be coated. Preferably, the binder (or sticker) is biodegradable. Preferably the binder or sticker is chosen to act as a matrix for the a tricarboxylic acid biphenylamide of formula I.

The binder (or sticker) may be selected from polyesters, polyether esters, polyanhy- drides, polyester urethanes, polyester amides; polyvinyl acetates; polyvinyl acetate copolymers; polyvinyl alcohols and tylose; polyvinyl alcohol copolymers; polyvinylpy- rolidones; polysaccharides, including starches, modified starches and starch derivatives, dextrins, maltodextrins, alginates, chitosanes and celluloses, cellulose esters, cellulose ethers and cellulose ether esters including ethylcelluloses, methylcelluloses, hydroxymethylcelluloses, hydroxypropylcelluloses and carboxymethylcellulose; fats; oils; proteins, including casein, gelatin and zeins; gum arabics; shellacs; vinylidene chloride and vinylidene chloride copolymers; lignosulfonates, in particular calcium Ng- nosulfonates; polyacrylates, polymethacrylates and acrylic copolymers; polyvinylacry- lates; polyethylene oxide; polybutenes, polyisobutenes, polystyrene, polyethylene- amines, polyethylenamides; acrylamide polymers and copolymers; polyhydroxyethyl acrylate, methylacrylamide monomers; and polychloroprene. In a particular embodiment, the binder is a thermoplastic polymer.

In a particular embodiment of the invention the seed treatment formulation contains at least one polyester, which, in particular, is selected from polylactides, partially aromatic polyesters (copolymers of terephthalic acid, adipic acid and aliphatic diols), polygly- colides, polyhydroxyalkanoates and polytartrates.

The amount of binder (or sticker) in the formulation can vary, but will be in the range of about 0.01 to about 25% of the total weight, more preferably from about 1 to about 15%, and even more preferably from about 5% to about 10%.

As mentioned above, the coating material can optionally also comprise a filler. The filler can be an absorbent or an inert filler, such as are known in the art, and may include wood flours, cereal flours, tree bark mill, wood meal and nut shell meal, sugars, in par- ticular polysaccharides, activated carbon, fine-grain inorganic solids, silica gels, silicates, clays, chalk, diatomaceous earth, calcium carbonate, magnesium carbonate, dolomite, magnesium oxide, calcium sulfate and the like. Clays and inorganic solids which may be used include calcium bentonite, kaolin, china clay, talc, perlite, mica, vermiculite, silicates, quartz powder, montmorillonite, attapulgite, bole, loess, lime- stone, lime and mixtures thereof. Sugars which may be useful include dextrin and mal- todextrin. Cereal flours include wheat flour, oat flour and barley flour. The filler may also comprise fertilizer substances such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and mixtures thereof.

The filler is selected so that it will provide a proper microclimate for the seed, for exam- pie the filler is used to increase the loading rate of the active ingredients and to adjust the control-release of the active ingredients. The filler can aid in the production or process of coating the seed. The amount of filler can vary, but generally the weight of the filler components will be in the range of about 0.05 to about 75% of the total weight, more preferably about 0.1 to about 50%, and even more preferably about 0.5% to 15%.

It is preferred that the binder (or sticker) be selected so that it can serve as a matrix for the active ingredients. While the binders disclosed above may all be useful as a matrix, it is preferred that a continuous solid phase of one or more binder compounds is formed throughout which is distributed as a discontinuous phase the active ingredients. Optionally, a filler and/or other components can also be present in the matrix. The term "matrix" is to be understood to include what may be viewed as a matrix system, a reservoir system or a microencapsulated system. In general, a matrix system consists of the active ingredients and a filler uniformly dispersed within a polymer, while a reservoir system consists of a separate phase comprising the active ingredients or salts thereof that are physically dispersed within a surrounding, rate-limiting, polymeric phase. Microencapsulation includes the coating of small particles or droplets of liquid, but also to dispersions in a solid matrix.

Especially if the active ingredients used in the coating have an oily type composition and little or no inert filler is present, it may be useful to hasten the drying process by drying the composition. This optional step may be accomplished by means well known in the art and can include the addition of calcium carbonate, kaolin or bentonite clay, perlite, diatomaceous earth, or any absorbent material that is added preferably concurrently with the active ingredients coating layer to absorb the oil or excess moisture. The amount of absorbent necessary to effectively provide a dry coating will be in the range of about 0.5 to about 10% of the weight of the seed.

Optionally, the coating material comprises a plasticizer. Plasticizers are typically used to make the film that is formed by the coating layer more flexible, to improve adhesion and spreadability, and to improve the speed of processing. Improved film flexibility is important to minimize chipping, breakage or flaking during storage, handling or sowing processes. Many plasticizers may be used; however, useful plasticizers include polyethylene glycol, oligomeric polyalkylene glycols, glycerol, alkylbenzylphthalates, in particular butylbenzylphthalate, glycol benzoates and related compounds. The amount of plasticizer in the coating layer will be in the range of from about 0.1 % by weight to about 20% by weight. Agents suitable for solid matrix priming materials which are useful in the present invention include polyacrylamide, starch, clay, silica, alumina, soil, sand, polyurea, polyacry- late, or any other material capable of absorbing or adsorbing the active ingredients for a time and releasing them into or onto the seed. It is useful to make sure that the active ingredients and the solid matrix material are compatible with each other. For example, the solid matrix material should be chosen so that it can release the active ingredients at a reasonable rate, for example over a period of minutes, hours, or days.

Penetration enhancers suitable for promoting seed imbibition include agriculturally ac- ceptable surface active compounds. The amount of penetration enhancers will usually not exceed 20% by weight, based on the total weight of the formulation. Preferably, the amount of penetration enhancers will be in the range from 2% to 20% by weight.

Colorants according to the invention are all dyes and pigments which are customary for such purposes. In this context, both pigments, which are sparingly soluble in water, and dyes, which are soluble in water, may be used. Examples which may be mentioned are the colorants, dyes and pigments known under the names Rhodamin B, C. I. Pigment Red 112 and C. I. Solvent Red 1 , Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1 , Pigment Blue 80, Pigment Yellow 1 , Pigment Yellow 13, Pig- ment Red 48:2, Pigment Red 48:1 , Pigment Red 57:1 , Pigment Red 53:1 , Pigment

Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red 51 , Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, Basic Red 108. The amount of colorants will usually not exceed 20% by weight of the formulation and preferably ranges from 1 to 15% by weight, based on the total weight of the formulation. It is generally preferred if the colorants are also active as repellents for warmblooded animals, e. g. iron oxide, Tiθ2, Prussian blue, anthraquinone dyes, azo dyes and metal phtalocyanine dyes.

Antifreezes which can be employed especially for aqueous formulations are in principle all those substances which lead to a depression of the melting point of water. Suitable antifreezes comprise alcohols such as methanol, ethanol, isopropanol, butanols, glycol, glycerine, diethylenglycol and the like. Typically, the amount of antifreeze will not exceed 20% by weight and frequently ranges from 1 to 15% by weight, based on the total weight of the formulation.

Gelling agents which are suitable are all substances which can be employed for such purposes in agrochemical compositions, for example cellulose derivatives, polyacrylic acid derivatives, xanthan, modified clays, in particular organically modified phyllosili- cates and highly-dispersed silicates. A particularly suitable gelling agent is carrageen (Satiagel^®). Usually, the amount of gelling agent will not exceed 5% by weight of the formulation and preferably ranges from 0.5 to 5% by weight, based on the total weight of the formulation.

Further auxiliary agents that may be present in the seed treatment formulation include solvents, wetters, dispersants, emulsifiers, surfactants, stabilizers, protective colloids, antifoams, and preservatives.

Examples of suitable solvents are water or organic solvents such as aromatic solvents (for example Solvesso^® products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used. However, according to a particular embodiment, the formulations of the present invention contain less than 10% by weight and preferably less than 6% by weight of said organic solvents.

Suitable surface-active compounds (wetters, dispersants, emulsifiers, surfactants, protective colloids) are as defined above.

Antifoams which can be employed are all those substances which inhibit the development of foam and which are conventionally used for formulating agrochemical active ingredients. Silicone antifoams, i.e. aqueous silicon emulsions (e.g. Silikon® SRE by Wacker or Rhodorsil® by Rhodia), long chain alcohols, fatty acids and salts thereof, e.g. and magnesium stearate are particularly suitable. Usually, the amount of antifoam will not exceed 3% by weight of the formulation and preferably ranges from 0.1 to 2% by weight, based on the total weight of the formulation.

Preservatives which can be employed are all preservatives used for such purposes in agrochemical compositions. Examples which may be mentioned are dichlorophene, isothiazolenes and isothiazolones such as 1 ,2-benzisothiazol-3(2H)-one, 2-methyl-2H-isothiazol-3-one-hydrochloride, 5-chloro-2-(4-chlorobenzyl)-3(2H)- isothiazolone, 5-chloro-2-methyl-2H-isothiazol-3-one, 5-chloro-2-methyl-2H-isothiazol- 3-one, 5-chloro-2-methyl-2H-isothiazol-3-one-hydrochloride, 4,5-dichloro-2-cyclohexyl- 4-isothiazolin-3-one, 4,5-dichloro-2-octyl-2H-isothiazol-3-one, 2-methyl-2H-isothiazol-3- one, 2-methyl-2H-isothiazol-3-one-calcium chloride complex, 2-octyl-2H-isothiazol-3- one and benzyl alcohol hemiformal. Usually, the amount of preservatives will not exceed 2% by weight of the formulation and preferably ranges from 0.01 to 1 % by weight, based on the total weight of the formulation.

Suitable formulations for the treatment of the growth medium, in particular the soil are, for example, granules and spray applications. The total application rates (i.e. the total amount of the active substances employed in accordance with the invention) for the treatment of seed are, for example, 0.1 to 1000 g, especially preferably 1 to 750 g, more preferably 5 to 200 g, even more preferably 10 to 150 g and in particular 20 to 150 g per 100 kg of seed.

The active substances employed in accordance with the invention can be formulated jointly or separately.

The use according to the invention, or the method according to the invention, result in a markedly reduced phytotoxic effect of the azole fungicide or of the combination of azole fungicide and anilide fungicide with an essentially unaltered or even improved fungicidal activity.

The invention furthermore relates to a composition comprising at least one azole fungicide, at least one gibberellin selected from gibberellin A₄, gibberellin A₇ and - preferably - a mixture thereof and optionally at least one anilide fungicide and also to a composition comprising at least one azole fungicide, at least one gibberellin and at least one anilide fungicide. As to preferred azole fungicides, gibberellins, anilide fungicides and their weight ratios, reference is made to the above remarks. In the latter composition, the gibberellin is preferably selected from gibberellin A₄, gibberellin A₇ and a mixture thereof and more preferably is a mixture of gibberellin A₄ and gibberellin A₇.

In a preferred embodiment of the invention, the composition according to the invention comprises difenoconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises epoxiconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises fluquinconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises flutriafol and gibberellin A4, gibberellin A₇ or preferably a mix- ture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises imazalil and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises metconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises prochloraz and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises propiconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises prothioconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises tebuconazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises triadimenol and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises triticonazole and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises difenoconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises epoxiconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises fluquinconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises flutriafol, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises imazalil, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises metconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises prochloraz, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises propiconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises prothioconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises tebuconazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof. In an alternatively preferred embodiment of the invention, the composition according to the invention comprises triadimenol, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In an alternatively preferred embodiment of the invention, the composition according to the invention comprises triticonazole, metalaxyl-M and gibberellin A₄, gibberellin A₇ or preferably a mixture thereof.

In a particularly preferred embodiment, the composition of the invention comprises triticonazole, a gibberellin selected from gibberellin A4, gibberellin A₇, and preferably a mixture of gibberellin A₄ and gibberellin A₇, and optionally also metalaxyl-M. In a spe- cific embodiment, the composition of the invention comprises triticonazole, metalaxyl-M and a mixture of gibberellin A₄ and gibberellin A₇.

The compositions according to the invention may take the form of a physical mixture of at least one of the above-defined fungicides with at least one of the above-defined gib- berellins. However, the composition may also be any combination of the active substances, where it is not necessary for the individual active substances to be present as a joint formulation.

An example of compositions according to the invention in which the at least one fungi- cide and the at least one gibberellin are not present in a joint formulation is a 2- component kit or a 3-component kit.

Accordingly, the present invention also relates to a 2-component kit, comprising a first component which comprises the at least one azole fungicide, optionally the at least one anilide fungicide, further a liquid or solid carrier and, if appropriate, at least one surface- active substance and/or at least one customary adjuvant, and a second component which comprises at least one gibberellin, a liquid or solid carrier and, if appropriate, at least one surface-active substance and/or at least one customary adjuvant.

The present invention also relates to a 3-component kit, comprising a first component which comprises the at least one azole fungicide, a liquid or solid carrier and, if appropriate, at least one surface-active substance and/or at least one customary adjuvant, a second component which comprises at least one anilide fungicide, a liquid or solid carrier and, if appropriate, at least one surface-active substance and/or at least one customary adjuvant, and a third component which comprises at least one gibberellin, a liquid or solid carrier and, if appropriate, at least one surface-active substance and/or at least one customary adjuvant.

Suitable liquid and solid carriers, surface-active substances and customary adjuvants are described hereinabove.

The compositions according to the invention can be present in formulated form, as described above, and/or they can contain the abovementioned, additional components (for example other active substances (fungicides, insecticides, herbicides, bactericides, nematicides, fertilizers, growth regulators and the like), adjuvants, oils, wetters and the like).

As regards the suitable and preferred weight ratios of the components present in the composition according to the invention, the application rates and the nature of their application, reference is made to what has been said above.

In comparison with corresponding compositions which, however, do not comprise any gibberellin, the compositions according to the invention are distinguished by a markedly reduced phytotoxicity. At the same time, their fungicidal activity is essentially unaltered or even improved. Accordingly, the invention also relates to the use of the composition according to the invention for the control of phytopathogenic fungi.

They are particularly suitable for controlling the following phytopathogenic fungi:

• Alternaria species on vegetables, oilseed rape, sugar beet, fruit and rice, for example A. solani or A. alternata on potatoes and tomatoes,

• Aphanomyces species on sugar beet and vegetables, • Bipolaris and Drechslera species on maize, cereals, rice and turf, for example D. maydis on maize,

• Blumeria graminis (powdery mildew) on cereals,

• Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grape vines,

• Bremia lactucae on lettuce, • Cercospora species on maize, soybeans, rice and sugar beet,

• Cochliobolus species on maize, cereals, rice (for example Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice),

• Colletotricum species on soybeans and cotton,

• Drechslera species and Pyrenophora species on cereals, rice, turf and maize, for example D. teres on barley or D. tritici-repentis on wheat,

• Esca on grape vines, caused by Phaeoacremonium chlamydosporium, Ph. Aleophi- lum, and Formitipora punctata (syn. Phellinus punctatus), • Exserohilum species on maize,

• Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

• Fusarium and Verticillium species on various plants, for example F. graminearum or F. culmorum on cereals or F. oxysporum on a multiplicity of plants such as, for ex- ample, tomatoes,

• Gaeumanomyces graminis on cereals,

• Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice),

• Grainstaining complex on rice,

• Helminthosporium species on maize and rice, • Michrodochium nivale on cereals,

• Mycosphaerella species on cereals, bananas and peanuts, for example M. graminicola on wheat or M. fijiensis on bananas,

• Peronospora species on cabbage and bulb plants, such as, for example, P. brassicae on cabbage or P. destructor on onions, • Phakopsora pachyrhizi and Phakopsora meibomiae on soybeans,

• Phomopsis species on soybeans and sunflowers,

• Phytophthora infestans on potatoes and tomatoes,

• Phytophthora species on a variety of plants such as, for example, P. capsici on capsicum, • Plasmopara viticola on grape vines,

• Podosphaera leucotricha on apples,

• Pseudocercosporella herpotrichoides on cereals,

• Pseudoperonospora species on a variety of plants such as, for example, P. cubensis on cucumbers or P. humili on hops, • Puccinia species on a variety of plants such as, for example, P. triticina,

P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus,

• Pyrenophora species on cereals,

• Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice, • Pyricularia grisea on turf and cereals,

• Pythium spp. on turf, rice, maize, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants, for example P. ultiumum on a variety of plants,

P. aphanidermatum on turf,

• Rhizoctonia species on cotton, rice, potatoes, turf, maize, oilseed rape, potatoes, sugar beet, vegetables and other plants, for example R. solani on beet and a variety of plants,

• Rhynchosporium secalis on barley, rye and triticale,

• Sclerotinia species on oilseed rape and sunflowers,

• Septoria tritici and Stagonospora nodorum on wheat, • Erysiphe (syn. Uncinula) necator on grape vines,

• Setospaeria species on maize and turf,

• Sphacelotheca reilinia on maize, • Thievaliopsis species on soybeans and cotton,

• Tilletia species on cereals,

• Ustilago species on cereals, maize and sugar beet, for example U. maydis on maize, and • Venturia species (scab) on apples and pears, for example V. inaequalis on apples.

In particular, the composition according to the invention is suitable for controlling soybean rust (Phakopsora pachyrhizi and Phakopsora meibomiae).

In a preferred embodiment, the composition according to the invention is a seed treatment composition. Consequently, it comprises, apart the above-defined active ingredients at least one auxiliary substance suitable for seed treatment compositions. Suitable one auxiliary substance suitable for seed treatment compositions are described above.

More preferably, the seed treatment formulation of the present invention is a seed coating formulation.

Such seed coating formulations comprise the above-listed active ingredients, at least one binder (or sticker) and optionally at least one further auxiliary agent that is selected from the group consisting of fillers and plasticizers.

Seed coating formulations comprising binders, fillers and/or plasticizers are well-known in the art. Seed coating formulations are disclosed, for example, in US 5,939,356, US 5,882,713, US 5,876,739, US 5,849,320, US 5,834,447, US 5,791 ,084, US 5,661 ,103, US 5,622,003, US 5,580,544, US 5,328,942, US 5,300,127, US 4,735,015, US 4,634,587, US 4,383,391 , US 4,372,080, US 4,339,456, US 4,272,417 and US 4,245,432, among others.

The coating formulations formed with the above-listed active ingredients are capable of effecting a slow rate of release of the active ingredients by diffusion or movement through the matrix into the seed or to the surrounding medium.

The present invention also provides a seed that has been treated by the method described above. It also provides a seed obtainable by the method described above.

Further, the present invention also provides a seed that has been treated with a seed treatment formulation described above, and in particular that is coated with the formulation or contains it. It also provides a seed obtainable by using the formulation described above.

The term "coated with and/or contains" here signifies that the active ingredients are for the most part on the surface of the seed at the time of application, although a greater or lesser part of them may penetrate into the seed, depending on the method of application. When the said seed is (re)planted, it may absorb the active ingredients.

Still further, the present invention relates to a seed, especially an unsown seed, which comprises the above-defined active ingredients.

According to one embodiment, such a seed has a coating which comprises the above- defined active ingredients. According to a further embodiment, in such a seed the ger- minable part and/or natural sheath, shell, pod and/or integument comprise(s) the above-defined active ingredients. Also the active ingredients can be present in both the coating and the germinable part and/or natural sheath, shell, pod and/or integument of the seed.

The seeds treated according to the invention may also be enveloped with a film over- coating to protect the active ingredients coating. Such overcoatings are known in the art and may be applied using conventional fluidized bed and drum film coating techniques.

The seeds of the present invention can be used for the propagation of plants. The seeds can be stored, handled, planted/sowed and tilled.

Unless indicated otherwise, all amounts in % by weight refer to the weight of the total composition (or formulation).

The following examples shall further illustrate the invention without limiting it.

Examples

1. Germination/emergence behavior of soybeans

The germination/emergence behavior of soybeans whose seeds have been treated with

• triticonazole (TTZ); or

• with a combination of triticonazole and gibberellin A3 (GA3)

was studied following the guidelines for germination testing according to the Association of Official Seed Analysts (AOSA, 2005). For this purpose, seeds of the variety AG 7601 were treated with the above-listed active compounds in the amounts given in the table below. Where more than one active substance was applied, the compounds were applied as a mixture. Triticonazole was employed as FS formulation in a concentration of 500 g/l; 25 g active substance per 100 kg seed. GA3 was applied in form of the commercial product Release from Valent BioSciences in a concentration of 33.8 g/l; 1.25 g active substance per 100 kg seed. The treatment was effected by means of a HEGE 11 seed treatment apparatus. 24 h after the treatment, the seeds were sown in FTS soil (a soil collected near Holly Springs, North Carolina, USA) or in a combination soil (Top soil:sand:MetroMix = 2:1 :1 ) and watered daily. 12 days after sowing, the number of seeds which had given rise to plants was examined. The results are shown in table 1 below. A value of 100% means that all sown seeds have given rise to plants.

Table 1 :

2. Germination/emergence behavior of soybeans

• triticonazole (TTZ); or

• with a combination of triticonazole and metalaxyl-M (m-M); or

• with a combination of triticonazole and gibberellin A3 (GA3) or

• with a combination of triticonazole, metalaxyl-M and gibberellin A3 (GA3)

was studied following the guidelines for germination testing according to the Association of Official Seed Analysts (AOSA, 2005). For this purpose, seeds of the variety AG 7601 were treated with the above-listed active compounds in the amounts given in the table below. The treatment was carried out as described in example 1. Triticonazole was employed as FS formulation in a concentration of 500 g/l; 25 g or 50 g active substance per 100 kg seed. Metalaxyl-M was applied in form of the commercial product Apron XL from Syngenta in a concentration of 360 g/l of mefenoxam; 3.75 g active substance per 100 kg seed. GA3 was applied in form of the commercial product Release from Valent BioSciences in a concentration of 33.8 g/l; 1.25 or 5 g active sub- stance per 100 kg seed. The seeds were sown 24 h after treatment in a combination soil (Top soil:sand:MetroMix = 2:1 :1 ). 10 days after sowing, the number of seeds which had given rise to plants was examined. The results are shown in table 2 below. A value of 100% means that all sown seeds have given rise to plants.

Table 2:

a.s. = active substance

3. Plant height/stunting of soybean plants

The stem length of soybean plants and the stand (number of living plants per row) whose seeds have been treated with

• with metalaxyl-M (m-M); or

• with a combination of triticonazole and metalaxyl-M (m-M); or

• with a combination of triticonazole, metalaxyl-M and gibberellin A₃ (GA₃); or

• with a combination of triticonazole, metalaxyl-M, gibberellin A₄ (GA₄) and gibberellin A₇ (GA₇) (GA₄ and GA₇ used as a 1 :1 mixture in form of the commercial product Provide) was determined. For this purpose, soybean seeds were treated and sowed according to example 1. 12, 15 and 16 days after sowing, the stem length (= length from the soil line to the meristem) of the plants was measured. The stand was counted 8 and 12 days after sowing. The results are compiled in table 3 below as mean values relative to the stem length or stand count of the treatment with metalaxyl-M alone (= 100 %).

Table 3

a.s. = active substance

Claims

We claim:

1. A method for controlling phytopathogenic fungi which comprises treating the seeds of a plant or the growing medium of the seeds with at least one azole fun- gicide in combination with at least one gibberellin and optionally at least one ani- lide fungicide.

2. The method as claimed in claim 1 , which comprises treating the seeds of a plant or the growing medium of the seeds with at least one azole fungicide in combina- tion with at least one gibberellin and at least one anilide fungicide.

3. The method as claimed in any of the preceding claims, for protecting a plant after germination from the attack of phytopathogenic fungi.

4. The method as claimed in claim 3, for protecting the plant after emergence from the attack of phytopathogenic fungi.

5. The method as claimed in any of the preceding claims, where the phytopathogenic fungi are selected from Phakopsora meibomiae and Phakopsora pachyr- hizi.

6. A method for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungi- cide and optionally with at least one anilide fungicide, which method comprises treating the seeds or the growing medium of the seeds with at least one azole fungicide and optionally at least one anilide fungicide in combination with at least one gibberellin.

7. The method as claimed in claim 6, for reducing or preventing the phytotoxic effect of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and with at least one anilide fungicide, which method comprises treating the seeds or the growing medium of the seeds with at least one azole fungicide, at least one anilide fungicide and at least one gibberellin.

8. The method as claimed in any of claims 6 or 7, for improving the germination and/or the emergence and/or the vigor of the plants.

9. The method as claimed in any of claims 6 or 7, for reducing or preventing the stunting effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and optionally with at least one anilide fungicide.

10. The method as claimed in any of the preceding claims, where the azole fungicide is triticonazole.

1 1. The method as claimed in any of the preceding claims, where the gibberellin is gibberellin A₄, gibberellin A7 or a mixture thereof.

12. The method as claimed in claim 11 , where a mixture of gibberellin A₄ and gibberellin A7 is used.

13. The method as claimed in any of the preceding claims, where the anilide fungicide is metalaxyl.

14. The method as claimed in any of the preceding claims, where the seed is a cereal seed or a leguminous seed.

15. The method as claimed in claim 14, where the seed is soybean seed.

16. The use of at least one gibberellin for reducing or preventing the phytotoxic effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and optionally at least one anilide fungicide.

17. The use as claimed in claim 16, for reducing or preventing the phytotoxic effect of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and at least one anilide fungicide.

18. The use as claimed in any of claims 16 or 17, for improving the germination and/or the emergence and/or the vigor of the plants.

19. The use as claimed in any of claims 16 or 17, for reducing or preventing the stunting effect of azole fungicides or of azole fungicides used in combination with anilide fungicides on plants the seeds or the growing medium of which have been treated with at least one azole fungicide and optionally with at least one anilide fungicide.

20. The use as claimed in any of claims 16 to 19, where the azole fungicide is tri- conazole.

21. The use as claimed in any of claims 16 to 20, where the gibberellin is gibberellin A₄, gibberellin A₇ or a mixture thereof.

22. The use as claimed in claim 21 , where a mixture of gibberellin A₄ and gibberellin A₇ is used.

23. The use as claimed in any of claims 16 to 22, where the anilide fungicide is metalaxyl.

24. A composition comprising at least one azole fungicide, at least one gibberellin selected from gibberellin A₄, gibberellin A₇ and a mixture thereof and optionally at least one anilide fungicide.

25. A composition comprising at least one azole fungicide, at least one gibberellin and at least one anilide fungicide.

26. The composition as claimed in claim 24 or 25, where the azole fungicide is triti— conazole.

27. The composition as claimed in any of claims 25 or 26, where the gibberellin is gibberellin A₄, gibberellin A₇ or a mixture thereof.

28. The composition as claimed in claim 24 or 27, comprising a mixture of gibberellin A₄ and gibberellin A₇.

29. The composition as claimed in any of claims 24 to 28, where the anilide fungicide is metalaxyl.