WO2022053640A1 - Mixtures containing calcium and magnesium phosphonate as pesticides - Google Patents

Abstract

The present invention relates to the use of mixtures comprising magnesium phosphonate and calcium phosphonate for combatting invertebrate pests. The invention also relates to a method for combatting invertebrate pests using said mixtures. The invention relates further to a mixture comprising in addition to magnesium phosphonate and calcium phosphonate at least one further pesticide B, and to the use of the mixture comprising magnesium phosphonate and calcium phosphonate as synergist for said pesticide B.

Description

Mixtures containing calcium and magnesium phosphonate as pesticides

The present invention relates to the use of mixtures comprising magnesium phosphonate and calcium phosphonate as pesticides for combatting invertebrate pests and to a method for combatting invertebrate pests using said mixtures. The invention relates also to a mixture comprising magnesium phosphonate and calcium phosphonate and moreover comprising at least one further pesticide B, and to the use of the mixture comprising magnesium phosphonate and calcium phosphonate as synergist for said pesticide B.

TECHNICAL BACKGROUND

Phosphonates are suitable phosphorus suppliers in agriculture and are thus described as fertilizers. They are moreover described to be useful as fungicides or as pesticides.

US 5,206,228 relates to the use of phosphorus acid and monoesters or salts thereof of the formula (I)

where R is OH or Ci-C4-alkoxy, M is a hydrogen atom (when R is OH) or an alkali metal, earth alkaline metal or aluminum cation, and n is 1 to 3, for controlling arthropod pests. While this document mentions that the compounds may be mixed salts of more than one metal cation, specific mixed salts are not described. Mixtures with other pesticides are also mentioned, but no specific mixture is described. Actually, the only tested compound is fosetyl-AL

In agriculture, a well-known problem is that repeated use of single pesticides often leads to resistance formation. Moreover, single pesticides are frequently not effective against all pests, or they are not effective under all environmental conditions. Nor are they always suitable for all crops or all types of treatment. There is also a need for pesticides which combine a fast effect and a long lasting activity. Another constant need in agriculture is the desire to reduce the dosage rates of pesticides in order to reduce or prevent environmental or toxicological damage while still ensuring effective pest control. Moreover, there is a constant need for compounds which are effective as pesticides or as synergists for known pesticides and which are safer and less toxic than the known agents. Specifically, there is a need for pesticides which do not have a negative impact on pollinators, such as bees. WO 2018/108822 relates to the use of mixtures containing secondary calcium and magnesium phosphonate as fungicide or fertilizer. A pesticidal effect is not mentioned.

It was an object of the present invention to provide mixtures which solve at least one of the listed problems, such as broadened spectrum of activity, reduced dosage rate, combined fast and long-lasting activity, reduced resistance, reduced toxicity, or enhanced safety, including environmental compatibility.

SUMMARY OF THE INVENTION

This object is achieved by the use of a mixture (mixture I) comprising magnesium phosphonate and calcium phosphonate (and optionally also sodium phosphonate and/or potassium phosphonate) for combating invertebrate pests.

The invention relates moreover to the use of a mixture obtainable by reacting dolomite and phosphonic acid, optionally in the presence of at least one of KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2COs and Na2O, for combatting invertebrate pests.

Furthermore, the invention relates to a method for combating invertebrate pests, which method comprises treating the invertebrate pests, their habitat, plants, plant propagation material or environment or material which is to be protected or rid from infestation by said pests with a pesticidally effective amount of a mixture as defined above or below.

The invention relates also to a method for protecting or relieving plants, plant propagation material or inanimate material from infestation with invertebrate pests, which method comprises treating the invertebrate pests, their habitat, plants, the environment in which the plants grow or are to grow, plant propagation material or environment or material which is to be protected or relieved from infestation by said pests with a pesticidally effective amount of a mixture as defined above or below; and to the use of said mixtures for protecting or relieving plants, plant propagation material or inanimate material from infestation with invertebrate pests.

The invention relates also to a mixture (mixture II) comprising as component A magnesium phosphonate and calcium phosphonate (and optionally also sodium phosphonate and/or potassium phosphonate); and as component B at least one further pesticide B, where the pesticide B is selected from the group consisting of:

B.1 acetylcholine esterase inhibitors selected from the class of carbamates which are in turn selected from the group consisting of alanycarb (B.1 .1), aldicarb (B.1 .2), bendiocarb (B.1.3), benfuracarb (B.1.4), butocarboxim (B.1.5), butoxycarboxi m (B.1.6), carbaryl (B.1.7), carbofuran (B.1.8), carbosulfan (B.1.9), ethiofencarb (B.1.10), fenobucarb (B.1.11), formetanate (B.1.12), furathiocarb (B.1.13), iso- procarb (B.1.14), methiocarb (B.1.15), methomyl (B.1.16), metolcarb (B.1.17), oxamyl (B.1.18), primicarb (B.1.19), propoxur (B.1.20), thiodicarb (B.1.21), thiofanox (B.1.22), triazamate (B.1.23), trimethacarb (B.1.24), XMC (B.1.25) and xy- lylcarb (B.1.26); or selected from the class of organophosphates which are in turn selected from the group consisting of acephate (B.1 .27), azamethiphos (B.1.28), azinphos-ethyl (B.1.29), azinphos-methyl (B.1.30), cadusafos (B.1.31), chloreth- oxyfos (B.1.32), chlorfenvinphos (B.1.33), chlormephos (B.1.34), chlorpyrifos (B.1.35), chlorpyrifos-methyl (B.1.36), coumaphos (B.1.37), cyanophos, (B.1.38) demeton-S-methyl (B.1.39), diazinon (B.1.40), dichlorvos/DDVP (B.1.41), dicrotophos (B.1.42), dimethoate (B.1.43), dimethylvinphos disulfoton (B.1.44), EPN (B.1.45), ethion (B.1.46), ethoprophos (B.1.47), famphur (B.1 .48), fenamiphos (B.1.49), fenitrothion (B.1.50), fenthion (B.1.51), fosthiazate (B.1.52), hepteno- phos (B.1.53), imicyafos (B.1.54), isofenphos (B.1.55), isopropyl O- (methoxyaminothio-phosphoryl) salicylate (B.1.56), isoxathion (B.1.57), malathion (B.1.58), mecarbam (B.1.59), methamidaphos (B.1.60), methidathion (B.1.61), mevinphos (B.1.62), monocrotophos (B.1.63), naled (B.1.64), omethoate (B.1.65), oxymethoate (B.1.66), oxydemeton-methyl (B.1.67), parathion (B.1.68), parathion-methyl (B.1.69), phenthoate (B.1.70), phorate (B.1.71), phosalone (B.1.72), phosmet (B.1.73), phosphamidon (B.1.74), phoxim (B.1.75), pirimiphos- methyl (B.1.76), profenofos (B.1.77), propetamphos (B.1.78), prothiofos (B.1.79), pyraclofos (B.1.80), pyridaphenthion (B.1.81), quinalphos (B.1.82), sulfotep (B.1.83), tebupirimfos (B.1.84), temephos (B.1.85), terbufos (B.1.86), tetrachlor- vinphos (B.1.87), thiometon (B.1.88), triazophos (B.1.89), trichlorfon (B.1.90) and vamidothion (B.1.91);

B.2 GABA-gated chloride channel blockers selected from the class of cyclodiene or- ganochlorines which are in turn selected from the group consisting of chlordane (B.2.1) and endosulfan (B.2.2); or selected from the class of phenylpyrazoles which are in turn selected from the group consisting of acetoprole (B.2.3), ethiprole (B.2.4), fipronil (B.2.5), pyrafluprole (B.2.6), pyriprole (B.2.7) and vaniliprole (B.2.8);

B.3 sodium channel modulators selected from the class of pyrethroids or pyrethrins which are in turn selected from the group consisting of acrinathrin (B.3.1), allethrin (B.3.2), d-cis-trans allethrin (B.3.3), d-trans allethrin (B.3.4), bifenthrin (B.3.5), beta-cyfluthrin (B.3.6), cyfluthrin (B.3.7), lambda-cyhalothrin (B.3.8), cy- permethrin (B.3.9), alpha-cypermethrin (B.3.10), bioallethrin (B.3.11), bioallethrin S-cyclopentenyl (B.3.12), bioresmethrin (B.3.13), cycloprothrin (B.3.14), cyfluthrin (B.3.15), beta-cyfluthrin (B.3.16), cyhalothrin (B.3.17), lambda-cyhalothrin (B.3.18), gamma-cyhalothrin (B.3.19), cypermethrin (B.3.20), alpha-cypermethrin (B.3.21), beta-cypermethrin (B.3.22), theta-cypermethrin (B.3.23), zeta- cypermethrin (B.3.24), cyphenothrin [(1 R)-trans- isomers] (B.3.25), deltamethrin (B.3.26), empenthrin [(EZ)- (1 R)- isomers] (B.3.27), esfenvalerate (B.3.28), etofenprox (B.3.29), fenpropathrin (B.3.30), fenvalerate (B.3.31), flucythrinate (B.3.32), flumethrin (B.3.33), tau-fluvalinate (B.3.34), halfenprox (B.3.35), ka- dathrin (B.3.36), metofluthrin (B.3.37), permethrin (B.3.38), phenothrin [(1 R)- trans- isomer] (B.3.39), prallethrin (B.3.40), profluthrin (B.3.41), pyrethrin (pyrethrum) (B.3.42), resmethrin (B.3.43), silafluofen (B.3.44), tefluthrin (B.3.45), tet- ramethrin [(1 R)- isomer] (B.3.46), tralomethrin (B.3.47) and transfluthrin (B.3.48); or selected from the group consistng of DDT (B.3.49) and methoxychlor (B.3.50);

B.4 nicotinic acetylcholine receptor (nAChR) competitive modulators selected from the class of neonicotinoids which are in turn selected from the group consisting of acetamiprid (B.4.1), clothianidin (B.4.2), dinotefuran (B.4.3), imidacloprid (B.4.4), nitenpyram (B.4.5), thiacloprid (B.4.6) and thiamethoxam (B.4.7); or selected from the group consisting of nicotine (B.4.8), sulfoxaflor (B.4.9), flupyradifurone (B.4.10) and triflumezopyrim (B.4.11);

B.5 nicotinic acetylcholine receptor (nAChR) allosteric modulators - Site I selected from the class of spinosyns which are in turn selected from the group consisting of spinetoram (B.5.1) and spinosad (B.5.2);

B.6 glutamate-gated chloride channel (GluCI) allosteric modulators selected from the group consisting of abamectin (B.6.1), emamectin benzoate (B.6.2), lepimectin (B.6.3) and milbemectin (B.6.4);

B.7 juvenile hormone mimics selected from the group consisting of hydroprene (B.7.1), kinoprene (B.7.2), methoprene (B.7.3), fenoxycarb (B.7.4) and pyriproxyfen (B.7.5);

B.8 miscellaneous non-specific (multi-site) inhibitors selected from the group consisting of methyl bromide (B.8.1) and other alkyl halides, chloropicrin (B.8.2), cryolite (B.8.3), sulfuryl fluoride (B.8.4), borax (B.8.5), boric acid (B.8.6), disodium octaborate (B.8.7), sodium borate (B.8.8), sodium metaborate (B.8.9), tartar emetic (B.8.10), dazomet (B.8.11) and metam (B.8.12);

B.9 chordotonal organ TRPV channel modulators selected from the group consisting of pymetrozine (B.9.1) and pyrifluquinazon (B.9.2);

B.10 mite growth inhibitors selected from the group consisting of clofentezine (B.10.1), diflovidazin (B.10.2), hexythiazox (B.10.3) and etoxazole (B.10.4);

B.11 microbial disruptors of insect midgut membranes selected from the group consisting of Bacillus thuringiensis (B.11 .1) and the insecticidal proteins they produce and Bacillus sphaericus (B.11 .2); B.12 inhibitors of mitochondrial ATP synthase selected from the group consisting of diafenthiuron (B.12.1), organotin miticides selected from the group consisting of azocyclotin (B.12.2), cyhexatin (B.12.3) and fenbutatin oxide (B.12.4); propargite (B.12.5) and tetradifon (B.12.6);

B.13 uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from the group consisting of chlorfenapyr (B.13.1), DNOC (B.13.2) and sul- fluramid (B.13.3);

B.14 nicotinic acetylcholine receptor (nAChR) channel blockers selected from the group consisting of bensultap (B.14.1), cartap hydrochloride (B.14.2), thiocyclam (B.14.3) and thiosultap-sodium (B.14.4);

B.15 inhibitors of chitin biosynthesis, type 0 selected from the group consisting of bis- trifluron (B.15.1), chlorfluazuron (B.15.2), diflubenzuron (B.15.3), flucycloxuron (B.15.4), flufenoxuron (B.15.5), hexaflumuron (B.15.6), lufenuron (B.15.7), no- valuron (B.15.8), noviflumuron (B.15.9), teflubenzuron (B.15.10) and triflumuron (B.15.11);

B.16 the inhibitor of chitin biosynthesis, type 1 buprofezin (B.16.1);

B.17 the moulting disruptor cyromazine (B.17.1);

B.18 ecdysone receptor agonists selected from the group consisting of chromafeno- zide (B.18.1), halofenozide (B.18.2), methoxyfenozide (B.18.3) and tebufenozide (B.18.4);

B.19 the octopamine receptor agonist amitraz (B.19.1);

B.20 mitochondrial complex III electron transport inhibitors selected from the group consisting of hydramethylnon (B.20.1), acequinocyl (B.20.2), fluacrypyrim (B.20.3) and bifenazate (B.20.4);

B.21 mitochondrial complex I electron transport inhibitors selected from the group consisting of fenazaquin (B.21.1), fenpyroximate (B.21.2), pyrimidifen (B.21.3), pyridaben (B.21 .4), tebufenpyrad (B.21 .5), tolfenpyrad (B.21 .6) and rotenone (B.21.7);

B.22 voltage-dependent sodium channel blockers selected from the group consisting of indoxacarb (B.22.1) and metaflumizone (B.22.2);

B.23 inhibitors of acetyl CoA carboxylase selected from the group consisting of spi- rodiclofen (B.23.1), spiromesifen (B.23.2), spiropidion (B.23.3) and spirotetramat (B.23.4);

B.24 mitochondrial complex IV electron transport inhibitors selected from the group consisting of aluminium phosphide (B.24.1), calcium phosphide (B.24.2), phosphine (B.24.3), zinc phosphide (B.24.4), calcium cyanide (B.24.5), potassium cyanide (B.24.6) and sodium cyanide (B.24.7);

B.25 mitochondrial complex II electron transport inhibitors selected from the group consisting of cyenopyrafen (B.25.1) and pyflubumide (B.25.2); B.26 ryanodine receptor modulators selected from the group consisting of chlorantraniliprole (B.26.1), cyantraniliprole (B.26.2), cyclaniliprole (B.26.3), flubendiamide (B.26.4) and tetraniliprole (B.26.5);

B.27 the chordotonal organ modulator of undefined target site flonicamide (B.27.1);

B.28 the GABA-gated chloride channel allosteric modulator fluxametamide (B.28.1);

B.29 compounds of unknown or uncertain mode of action selected from the group consisting of azadi rachtin (B.29.1), benzoximate (B.29.2), bromopropylate (B.29.3), chinomethionat (B.29.4), dicofol (B.29.5) and pyridalyl (B.29.6);

B.30 Baculoviruses selected from the group consisting of Cydia pomonella GV (B.30.1), Thaumatotibia leucotreta GV (B.30.2), Anticarsia gemmatalis MNPV (B.30.3) and Helicoverpa armigera NPV (B.30.4);

B.31 the nicotinic acetylcholine receptor (nAChR) allosteric modulator - site II GS- omega/kappa HXTX-Hv1a peptide (B.31.1);

B.32 bacterial agents (non-Bt) of unknown or uncertain mode of action selected from the group consisting of Burkholderia spp (B.32.1) and Wolbachie pipientis (Zap) (B.32.2);

B.33 botanical essence including synthetic, extracts and unrefined oils with unknown or uncertain mode of action selected from the group consisting of Chenopodium ambrosioides near ambrosioides extract (B.33.1), fatty acid monoesters with glycerol (B.33.2) or propanediol (B.33.3) and Neem oil (B.33.4);

B.34 fungal agents of unknown or uncertain mode of action selected from the group consisting of Beauveria bassiana strains (B.34.1), Metarhizium anisopliae strain F52 (B.34.2) and Paecilomyces fumosoroseus Apopka strain 97 (B.34.3); and

B.35 non-specific mechanical disruptors selected from the group consisting of Diatomaceous earth (B.35.1) and kaolin (B.35.2).

The invention relates moreover to an agricultural composition comprising such a mixture II and at least one inert liquid and/or solid agriculturally acceptable carrier.

The invention further relates to the use of such mixtures II for combating invertebrate pests.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

In mixtures of component A (mixture comprising magnesium phosphonate and calcium phosphonate, and optionally also sodium phosphonate and/or potassium phosphonate) and pesticide B, the term "mixture" does not necessarily require the component A and the pesticide B to be present as a physical mixture when applied, but can constitute any desired combination of the two components in which they are not necessarily formulated together. The component A and the pesticide B can thus also be applied separately. In this case, they have of course to be applied in close correlation in terms of space and time. One example of a composition in which component A and pesticide B are not present as a physical mixture is a two-component kit comprising a first component which comprises the component A and a second component which comprises the pesticide B.

In a specific embodiment, the mixture of component A and pesticide B is a physical mixture.

The same applies to the mixture I of magnesium phosphonate and calcium phosphonate (also in the form of component A in mixtures II); i.e. the term "mixture" does not necessarily require magnesium phosphonate and calcium phosphonate to be present as a physical mixture when applied, but can constitute any desired combination of the two components in which they are not necessarily formulated together. Magnesium phosphonate and calcium phosphonate can thus also be applied separately. In this case, they have of course to be applied in close correlation in terms of space and time. One example of a composition in which magnesium phosphonate and calcium phosphonate are not present as a physical mixture is a two-component kit comprising a first component which comprises magnesium phosphonate and a second component which comprises calcium phosphonate.

Preferably, however, the mixture I of magnesium phosphonate and calcium phosphonate is a physical mixture.

The same applies if the mixture I of magnesium phosphonate and calcium phosphonate also comprises one or both of sodium and potassium phosphonate, i.e. the term "mixture" does not necessarily require magnesium phosphonate, calcium phosphonate and the one or both of sodium and potassium phosphonate to be present as a physical mixture when applied, but can constitute any desired combination of the three or four components in which they are not necessarily formulated together. The phosphonates can thus also be applied separately. In this case, they have of course to be applied in close correlation in terms of space and time. Preferably, however, the mixture I of magnesium phosphonate, calcium phosphonate and one or both of sodium and potassium phosphonate is a physical mixture. In terms of the present invention, phosphonic acid and phosphorous acid are used synonymously and designate H3PO3 (depicted either as H-P(=O)(OH)2 or as its tautomer P(OH)₃).

In terms of the present invention, phosphonate designates phosphonic acid salts (also known as phosphites).

Phosphonates in the sense of phosphonic acid salts can be primary or secondary. In primary phosphonates one proton is formally replaced by a cationic equivalent (M⁺(H2PC>3)’; M⁺ is a cationic equivalent, such as a metal ("Met") cation equivalent (Met^x+)i/_x or an ammonium cation NH4⁺), and in secondary phosphonates, two protons are replaced by a cationic equivalent ((M⁺)2(HPC>3)² ). By way of example, secondary calcium phosphonate is Ca(HPC>3), secondary magnesium phosphonate is Mg(HPOs), secondary sodium phosphonate is Na2(HPOs) and secondary potassium phosphonate is K₂(HPO₃), while primary calcium phosphonate is Ca(H2PO3)2, primary magnesium phosphonate is Mg(H2PO3)2, primary sodium phosphonate is Na(H2POs) and primary potassium phosphonate is K(H2POs).

If used without the specification whether primary or secondary, the term "phosphonate" (phosphonic acid salt), encompasses both forms.

The pesticides B are known in the art, and also commercially available. They are described, for example, in The Pesticide Manual, 16^th Edition, C. MacBean, British Crop Protection Council (2013); see also http://bcpcdata.com/pesticide-manual.html, and in The Compendium of Pesticide Common Names, (http://www.alanwood.net/pesticides). Their grouping in groups B.1 to B.35 is along the mode of action classification of the Insecticide Resistance Action Committee (IRAC).

A dispersion is generally a system in which particles are dispersed in a continuous phase of a different composition (or state). Examples are solutions, suspensions or colloids. A solution is a homogeneous mixture in a liquid continuous phase. A suspension is a heterogeneous mixture containing solid particles in which the solute particles are not dissolved, but suspended throughout the bulk of the medium. Generally, the suspended particles are visible to the naked eye or at least under an optical microscope. Unlike in a colloid, the suspended particles will settle over time if left undisturbed. A colloid is a mixture in which one substance of microscopically dispersed insoluble particles is suspended throughout another substance. Unlike a solution, whose solute and solvent constitute only one phase, a colloid has a dispersed phase (the suspended particles) and a continuous phase (the medium of suspension). To qualify as a colloid and to distinguish from suspensions, the mixture must be one that does not settle or would take a very long time to settle appreciably.

"Aqueous dispersion", as used below in context with suitable formulations of the active compounds, includes, apart from dispersions containing pure water as dispersing medium, also dispersions containing buffered aqueous solutions or mixtures of water with lower alkanols as dispersing medium, such a methanol, ethanol, n-propanol or isopro- panol. If a mixture of water and an alkanol is used, the weight ratio of water to alkanol is preferably in the range of from 100:1 to 1 :1 , more preferably from 50:1 to 2:1 and in particular from 20:1 to 10:1. Preferably, however, the aqueous dispersion contains water or a buffered aqueous solution as dispersing medium (i.e. no alkanol).

Analogously, "aqueous solution", as used below in context with suitable formulations of the active compounds, includes, apart from solutions containing pure water as dispersing medium, also solutions containing buffered aqueous solutions or mixtures of water with lower alkanols as dispersing medium, such a methanol, ethanol, n-propanol or isopropanol. If a mixture of water and an alkanol is used, the weight ratio of water to alkanol is preferably in the range of from 100:1 to 1 :1 , more preferably from 50:1 to 2:1 and in particular from 20:1 to 10:1. Preferably, however, the aqueous solution contains water or a buffered aqueous solution as dispersing medium (i.e. no alkanol).

Embodiments

The below remarks with respect to preferred embodiments of the composition of mixture I, pesticides B, weight ratios of components A and B, pests to be treated, crops and materials to be protected and the like apply both alone as well as in any combination with each other. Where applicable, and unless specified otherwise, they apply both in context with the pesticidal uses of the invention and the method of the invention and also with the mixtures of the invention, as far as applicable.

According to the invention, a mixture I of magnesium phosphonate and calcium phos- phonate is used, where the mixture optionally also contains sodium phosphonate and/or potassium phosphonate.

Sodium phosphonate and potassium phosphonate in the mixture comprising magnesium phosphonate and calcium phosphonate act inter alia as a disintegrant. A disinte- grant is a material present in a composition which makes it disintegrate (and thus release the active ingredient) upon contact with water. Since the mixture of magnesium phosphonate and calcium phosphonate can be applied in aqueous phase, it is advan- tageous to provide a composition which disintegrates expediently and gives a fine dispersion in water. Usual disintegrants are selected from the group consisting of KHCO3, K2CO3, KOH, NaHCOs, Na2CO3, NaOH, microcrystalline cellulose and pregelatinized starch. These disintegrants can also be used in combination with the mixture of magnesium phosphonate and calcium phosphonate, but given that sodium phosphonate and potassium phosphonate also have a pesticidal activity and given that they can be easily prepared in situ with magnesium phosphonate and calcium phosphonate (e.g. by simply subjecting carbonates, hydroxides or oxides or mixed form thereof of all desired cations to the reaction with phosphonic acid), it is of course expedient to use sodium phosphonate and/or potassium phosphonate for this purpose.

The combination with of sodium phosphonate and/or potassium phosphonate with a calcium and/or magnesium phosphonate has advantageous properties, resulting in combined long-term and fast pesticidal action. Both potassium and sodium salts interact with the formation of calcium and magnesium phosphonates, resulting in significantly smaller particle size and thus an increased surface, improving biological availability and decreasing the wash-off and loss from leaves by rain.

Therefore, in a preferred embodiment, mixture I comprises magnesium phosphonate, calcium phosphonate and at least one of sodium phosphonate and potassium phosphonate.

Preferably, the mixture I comprising magnesium phosphonate and calcium phosphonate comprises at least one of primary magnesium phosphonate and primary calcium phosphonate and at least one of secondary magnesium phosphonate and secondary calcium phosphonate. In other words, the mixture comprises at least one primary phosphonate and at least one secondary phosphonate. This preferred mixture optionally comprises also sodium phosphonate and/or potassium phosphonate. In a specific embodiment, this preferred mixture comprises at least one of sodium phosphonate and potassium phosphonate.

In the mixture I comprising magnesium phosphonate and calcium phosphonate, be it a mixture of only primary phosphonates, of only secondary phosphonates or of both primary and secondary phosphonates, the molar ratio of calcium phosphonate to magnesium phosphonate is preferably of from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, in particular from 2:1 to 1 :2, specifically from 1.5:1 to 1 :1.5. Specifically, it is approximately 1 :1 . "Approximately" in this context includes deviations as they occur from weighing errors or from fluctuations in the composition of the salts used for producing the mix- ture. Such deviations are generally in the range of at most ±10%, preferably of at most ±5%.

Alternatively expressed, the molar ratio of the overall amount of calcium ions in the mixture I comprising magnesium phosphonate and calcium phosphonate to the overall amount of magnesium ions in the mixture comprising magnesium phosphonate and calcium phosphonate is preferably of from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, in particular from 2:1 to 1 :2, more particularly from 1.5:1 to 1 :1.5. Specifically, it is approximately 1 :1 . As already defined above, "approximately" in this context includes deviations as they occur from weighing errors or from fluctuations in the composition of the salts used for producing the mixture.

In particular, in mixtures I, the mixture of magnesium phosphonate and calcium phosphonate comprises at least one of primary magnesium phosphonate and primary calcium phosphonate and at least one of secondary magnesium phosphonate and secondary calcium phosphonate, and the molar ratio of (overall) calcium phosphonate to (overall) magnesium phosphonate is preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, in particular from 2:1 to 1 :2, specifically from 1 .5:1 to 1 :1 .5 and is very specifically approximately 1 :1. Alternatively expressed, in particular, in mixtures I, the mixture of magnesium phosphonate and calcium phosphonate comprises at least one of primary magnesium phosphonate and primary calcium phosphonate and at least one of secondary magnesium phosphonate and secondary calcium phosphonate, and the molar ratio of calcium ions to magnesium ions is preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, in particular from 2:1 to 1 :2, specifically from 1.5:1 to 1 :1.5 and is very specifically approximately 1 :1 .

If the mixture I of magnesium phosphonate and calcium phosphonate also comprises sodium phosphonate and/or potassium phosphonate, the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is generally from 20:1 to 1 :20, preferably from 10:1 to 1 :10, more preferably from 2:1 to 1 :10, even more preferably from 2:1 to 1 :5, in particular from 1 :1 to 1 :5, specifically from 1 :1 to 1 :4.

Alternatively, in the mixture of magnesium phosphonate, calcium phosphonate and one or both of sodium phosphonate and potassium phosphonate, the molar ratio of the overall amount of sodium ions and potassium ions to the overall amount of magnesium ions and calcium ions is generally from 20:1 to 1 :20, preferably of from 10:1 to 1 :10, more preferably from 2:1 to 1 :10, even more preferably from 2:1 to 1 :5, in particular from 1 :1 to 1 :5, specifically from 1 :1 to 1 :4. In another embodiment, the use and method of the invention comprise the use/application of a mixture I, which, in addition to calcium and magnesium phospho- nate and the optional sodium and/or potassium phosphonate (termed in the following component A) also comprises a further pesticide B (component B) which is selected from the group consisting of:

B.1 acetylcholine esterase inhibitors selected from the class of carbamates which are in turn selected from the group consisting of alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxi m, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, primicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or selected from the class of organophosphates which are in turn selected from the group consisting of acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chloreth- oxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, couma- phos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidaphos, methidathion, mevinphos, monocroto- phos, naled, omethoate, oxymethoate, oxydemeton-methyl, parathion, parathion- methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pi- rimiphos-methyl, profenofos , propetamphos, prothiofos, pyraclofos, pyri- daphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlor- vinphos, thiometon, triazophos, trichlorfon, and vamidothion;

B.2 GABA-gated chloride channel blockers selected from the class of cyclodiene or- ganochlorines which are in turn selected from the group consisting of chlordane and endosulfan; or selected from the class of phenylpyrazoles which are in turn selected from the group consisting of acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole and vaniliprole;

B.3 sodium channel modulators selected from the class of pyrethroids or pyrethrins which are in turn selected from the group consisting of acrinathrin, allethrin, d-cis- trans allethrin, d-trans allethrin, bifenthrin, beta-cyfluthrin, cyfluthrin, lambda- cyhalothrin, cypermethrin, alpha-cypermethrin, bioallethrin, bioallethrin S- cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, th eta-cy permethrin, zeta-cypermethrin, cyphenothrin [(1 R)-trans- isomers], deltamethrin, empenthrin [(EZ)- (1 R)- isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, kadathrin, metofluthrin, permethrin, phenothrin [(1 R)-trans- isomer], prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tet- ramethrin [(1 R)- isomer], tralomethrin and transfluthrin; or selected from the group consistng of DDT and methoxychlor;

B.4 nicotinic acetylcholine receptor (nAChR) competitive modulators selected from the class of neonicotinoids which are in turn selected from the group consisting of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or selected from the group consisting of nicotine, sulfoxaflor, flupyradifurone and triflumezopyrim;

B.5 nicotinic acetylcholine receptor (nAChR) allosteric modulators - Site I selected from the class of spinosyns which are in turn selected from the group consisting of spinetoram and spinosad;

B.6 glutamate-gated chloride channel (GluCI) allosteric modulators selected from the group consisting of abamectin, emamectin benzoate, lepimectin and milbemectin;

B.7 juvenile hormone mimics selected from the group consisting of hydroprene, ki- noprene, methoprene, fenoxycarb and pyriproxyfen;

B.8 miscellaneous non-specific (multi-site) inhibitors selected from the group consisting of methyl bromide and other alkyl halides, chloropicrin, cryolite, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium borate, sodium metaborate, tartar emetic, dazomet and metam;

B.9 chordotonal organ TRPV channel modulators selected from the group consisting of pymetrozine and pyrifluquinazon;

B.10 mite growth inhibitors selected from the group consisting of clofentezine, di- flovidazin, hexythiazox and etoxazole;

B.11 microbial disruptors of insect midgut membranes selected from the group consisting of Bacillus thuringiensis and the insecticidal proteins they produce and Bacillus sphaericus;

B.12 inhibitors of mitochondrial ATP synthase selected from the group consisting of diafenthiuron, organotin miticides selected from the group consisting of azocyclotin, cyhexatin and fenbutatin oxide; propargite and tetradifon;

B.13 uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from the group consisting of chlorfenapyr, DNOC and sulfluramid;

B.14 nicotinic acetylcholine receptor (nAChR) channel blockers selected from the group consisting of bensultap, cartap hydrochloride, thiocyclam and thiosultap- sodium;

B.15 inhibitors of chitin biosynthesis, type 0 selected from the group consisting of bis- trifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron;

B.16 the inhibitors of chitin biosynthesis, type 1 buprofezin; B.17 the moulting disruptor cyromazine;

B.18 ecdysone receptor agonists selected from the group consisting of chromafeno- zide, halofenozide, methoxyfenozide and tebufenozide;

B.19 the octopamine receptor agonist amitraz;

B.20 mitochondrial complex III electron transport inhibitors selected from the group consisting of hydramethylnon, acequinocyl, fluacrypyrim and bifenazate;

B.21 mitochondrial complex I electron transport inhibitors selected from the group consisting of fenazaquin, fen pyroxi mate, pyrimidifen, pyridaben, tebufenpyrad, tolf- enpyrad and rotenone;

B.22 voltage-dependent sodium channel blockers selected from the group consisting of indoxacarb and metaflumizone;

B.23 inhibitors of acetyl CoA carboxylase selected from the group consisting of spi- rodiclofen, spiromesifen, spiropidion and spirotetramat;

B.24 mitochondrial complex IV electron transport inhibitors selected from the group consisting of aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, calcium cyanide, potassium cyanide and sodium cyanide;

B.25 mitochondrial complex II electron transport inhibitors selected from the group consisting of cyenopyrafen and pyflubumide;

B.26 ryanodine receptor modulators selected from the group consisting of chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole;

B.27 the chordotonal organ modulator of undefined target site flonicamide;

B.28 the GABA-gated chloride channel allosteric modulator fluxametamide;

B.29 compounds of unknown or uncertain mode of action selected from the group consisting of azadi rachtin, benzoximate, bromopropylate, chinomethionat, dicofol, pyridalyl, sulfur and lime sulfur;

B.30 Baculoviruses selected from the group consisting of Cydia pomonella GV, Thau- matotibia leucotreta GV, Anticarsia gemmatalis MNPV and Helicoverpa armigera NPV;

B.31 the nicotinic acetylcholine receptor (nAChR) allosteric modulator - site II GS- omega/kappa HXTX-Hv1a peptide;

B.32 bacterial agents (non-Bt) of unknown or uncertain mode of action selected from the group consisting of Burkholderia spp and Wolbachie pipientis (Zap);

B.33 botanical essence including synthetic, extracts and unrefined oils with unknown or uncertain mode of action selected from the group consisting of Chenopodium ambrosioides near ambrosioides extract, fatty acid monoesters with glycerol or propanediol and Neem oil; B.34 fungal agents of unknown or uncertain mode of action selected from the group consisting of Beauveria bassiana strains, Metarhizium anisopliae strain F52 and Paecilomyces fumosoroseus Apopka strain 97; and

B.35 non-specific mechanical disruptors selected from the group consisting of Diatomaceous earth and kaolin.

The weight ratio of the overall amount of component A (calculated as dry matter of phosphonate salts) to the overall amount of pesticide B is preferably of from 100:1 to 1 :100, more preferably from 50:1 to 1 :10, even more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2. “Calculated as dry matter” means here and in any other instance where this term is used that the given ratios relate to component A in solid form, i.e. containing less than 10% by weight, preferably less than 5% by weight, in particular less than 2% by weight of any solvent (generally water). Alternatively expressed, the weight ratio of the overall amount of calcium phosphonate, magnesium phosphonate, sodium phosphonate, if present, and potassium phosphonate, if present, to the overall amount of pesticide B is preferably of from 100:1 to 1 :100, more preferably from 50:1 to 1 :10, even more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2.

The following Table 1 represents preferred combinations of the component A and pesticide B in mixtures according to the invention. Following abbreviations are used: A.1 mixture of magnesium phosphonate and calcium phosphonate

A.2 mixture of primary magnesium phosphonate and primary calcium phosphonate A.3 mixture of secondary magnesium phosphonate and secondary calcium phosphonate

A.4 mixture containing at least one of primary magnesium phosphonate and primary calcium phosphonate and containing at least one of secondary magnesium phosphonate and secondary calcium phosphonate

A.5 mixture of primary magnesium phosphonate and secondary calcium phosphonate A.6 mixture of secondary magnesium phosphonate and primary calcium phosphonate A.7 mixture of primary magnesium phosphonate, primary calcium phosphonate, secondary magnesium phosphonate and secondary calcium phosphonate

A.8 mixture of magnesium phosphonate, calcium phosphonate and sodium phosphonate

A.9 mixture of magnesium phosphonate, calcium phosphonate and potassium phosphonate

A.10 mixture of magnesium phosphonate, calcium phosphonate, sodium phosphonate and potassium phosphonate The abbreviations for pesticides B have already been assigned above, except for sulfur, which is termed B.29.7 in the following and lime sulfur, which is termed B.29.8 in the following. Table 1

In the mixtures of Table 1, agent A (calculated as dry matter of phosphonates) and pesticide B are present in a weight ratio of preferably from 100:1 to 1 : 100, more preferably from 50:1 to 1 :10, even more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2. The same applies to the following embodiments.

In an embodiment of the mixtures of Table 1 , agent A is A.1 .

In an embodiment of the mixtures of Table 1 , agent A is A.1 , where magnesium phos- phonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.1 , where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1 , agent A is A.1 , where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of Table 1 , agent A is A.1 , where magnesium phos- phonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of Table 1 , agent A is A.1 , where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1. In an embodiment of the mixtures of Table 1 , agent A is A.2. In an embodiment of the mixtures of Table 1, agent A is A.2, where magnesium phos- phonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1, agent A is A.2, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1, agent A is A.2, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of Table 1 , agent A is A.2, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of T able 1 , agent A is A.2, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1.

In an embodiment of the mixtures of Table 1 , agent A is A.3.

In an embodiment of the mixtures of Table 1 , agent A is A.3, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.3, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1 , agent A is A.3, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of T able 1 , agent A is A.3, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of Table 1 , agent A is A.3, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1.

In an embodiment of the mixtures of Table 1 , agent A is A.4.

In an embodiment of the mixtures of Table 1 , agent A is A.4, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.4, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1 , agent A is A.4, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of T able 1 , agent A is A.4, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of T able 1 , agent A is A.4, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1.

In an embodiment of the mixtures of Table 1 , agent A is A.5.

In an embodiment of the mixtures of Table 1 , agent A is A.5, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.5, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1 , agent A is A.5, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of T able 1 , agent A is A.5, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of Table 1 , agent A is A.5, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1.

In an embodiment of the mixtures of Table 1, agent A is A.6.

In an embodiment of the mixtures of Table 1, agent A is A.6, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1, agent A is A.6, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1 , agent A is A.6, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of T able 1 , agent A is A.6, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of T able 1 , agent A is A.6, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1.

In an embodiment of the mixtures of Table 1 , agent A is A.7.

In an embodiment of the mixtures of Table 1 , agent A is A.7, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.7, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5. In an embodiment of the mixtures of Table 1 , agent A is A.7, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2. In an embodiment of the mixtures of T able 1 , agent A is A.7, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5. In an embodiment of the mixtures of T able 1 , agent A is A.7, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1.

In an embodiment of the mixtures of Table 1 , agent A is A.8.

In an embodiment of the mixtures of Table 1 , agent A is A.8, where the molar ratio of sodium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10.

In an embodiment of the mixtures of Table 1 , agent A is A.8, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10 and the molar ratio of sodium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.8, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5 and the molar ratio of sodium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.8, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2 and the molar ratio of sodium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1, agent A is A.8, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5 and the molar ratio of sodium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.8, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1 and the molar ratio of sodium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10.

In an embodiment of the mixtures of Table 1, agent A is A.9.

In an embodiment of the mixtures of Table 1, agent A is A.9, where the molar ratio of potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10.

In an embodiment of the mixtures of Table 1, agent A is A.9, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10 and the molar ratio of potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.9, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5 and the molar ratio of potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.9, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2 and the molar ratio of potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.9, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5 and the molar ratio of potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.9, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1 and the molar ratio of potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10.

In an embodiment of the mixtures of Table 1 , agent A is A.10.

In an embodiment of the mixtures of Table 1 , agent A is A.10, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 10:1 to 1 :10 and the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.10, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 5:1 to 1 :5 and the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.10, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 2:1 to 1 :2 and the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1 , agent A is A.10, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of from 1.5:1 to 1 :1.5 and the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10. In an embodiment of the mixtures of Table 1, agent A is A.10, where magnesium phosphonate and calcium phosphonate are contained in a molar ratio of approximately 1 :1 and the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 10:1 to 1 :10.

The phosphonates used in mixtures I or in mixtures II in component A are principally known and can be prepared by standard reactions. The phosphonates (phosphonic acid salts), i.e. calcium phosphonate and magnesium phosphonate, as well as sodium phosphonate and potassium phosphonate, if present, can for example be prepared by the reaction of the respective metal carbonate, oxide or hydroxide with phosphonic acid. Suitable methods are described in WO2018/108822 or WO2019/238675.

For instance, the respective metal carbonates, oxides or hydroxides are mixed with phosphonic acid. If desired, a premix of all starting salts can be prepared before mixing with phosphonic acid. Phosphonic acid can be used as a solid or as an aqueous solution. Reaction generally starts instantaneously in the presence of water, which generally becomes manifest by gas evolution or foaming if at least one of the metal salts is used as a carbonate, and/or by exothermy. If all starting materials are used in solid form, it might be expedient to initiate the reaction by the addition of a small amount of water (on a laboratory scale a few drops are sufficient). While the addition of further water is principally not necessary (due to the formation of reaction water a slurry forms anyway as the reaction proceeds), it might nevertheless be expedient to add some water in the course of the reaction to keep the mixture better stirrable and ensure complete reaction. The reaction can of course also be carried out in solution (generally in an aqueous medium), but given that after completion of the reaction water is generally removed in order to save storage and transport costs, it is of course expedient to use as little water as possible during the reaction. Although the reaction is principally exothermic, it may be expedient to heat the reaction mixture, e.g. to 50 to 90°C or 60 to 80°C, in order to accelerate the reaction or ensure complete conversion.

The mixture of magnesium phosphonate and calcium phosphonate is preferably obtainable by reacting phosphonic acid with dolomite.

The term "dolomite" designates on the one hand a sedimentary carbonate rock ("dolostone" or "dolomite rock") that contains a high percentage (mostly at least 90% by weight, based on the total weight of the dolomite rock) of the mineral dolomite, CaMg(CC>3)2. On the other hand, as understood from the preceding remarks, the term "dolomite" also designates only the mineral dolomite of the elemental formula CaMg(CO3)2.

In terms of the present invention, the term "dolomite", unless specified otherwise, does not refer to dolomite rock, but refers to the mineral dolomite of the elemental formula CaMg(CC>3)2 (also termed “non-calcinated dolomite” or “dolomite in the proper sense” in the following), as it occurs in dolomite rock, and also includes partially calcinated dolomite, fully calcinated dolomite and mixtures of these forms. In partially calcinated dolomite, a part or all of the magnesium carbonate is converted into magnesium oxide. This is obtained by heating dolomite to ca. 850°C. Partially calcinated dolomite can be characterized by the formula Ca(CC>3) / a x MgO / b x Mg(CC>3), where a and b are fractions of 1 , so that a + b = 1 , where a is from 0.5 to 1 , preferably from 0.8 to 1 , in particular from 0.9 to 1 , and b is from 0 to 0.5, preferably from 0 to 0.2, in particular from 0 to 0.1 . In a specific embodiment, partially calcinated dolomite has the formula Ca(CC>3) 1 0.9 x MgO 10.1 x Mg(COs). Fully calcinated dolomite has the elemental formula CaMgO2.

Suitable methods for preparing mixtures of magnesium phosphonate and calcium phosphonate from dolomite are described, for example in WO2018/108822 or WO2019/238675.

For instance, in analogy to what has already been said above, dolomite and, if desired, at least one of KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2CO3 and Na2O are mixed with phosphonic acid. If desired, a premix of all starting salts can be prepared before mixing with phosphonic acid. Phosphonic acid can be used as a solid or as an aqueous solution. Reaction generally starts instantaneously in the presence of water, which generally becomes manifest by gas evolution or foaming if non-calcinated dolomite (dolomite in the proper sense) partially calcinated dolomite and/or at least one of KHCO3, K2CO3, NaHCOs and Na2COs is used, and/or by exothermy. If all starting materials are used in solid form, it might be expedient to initiate the reaction by the addition of a small amount of water (on a laboratory scale a few drops are sufficient). While the addition of further water is principally not necessary, since due to the formation of reaction water a slurry forms as the reaction proceeds, it might nevertheless be expedient to add some water in the course of the reaction to keep the mixture better stirrable and ensure complete reaction. The reaction can of course also be carried out in solution (generally in an aqueous medium), but given that after completion of the reaction water is generally removed in order to save storage and transport costs, it is of course expedient to use as little water as possible during the reaction. Although the reaction is principally exothermic, it may be expedient to heat the reaction mixture, e.g. to 50 to 90°C or 60 to 80°C, in order to accelerate the reaction or ensure complete conversion.

Preferably, dolomite and phosphonic acid are reacted in a molar ratio of from 1 :1 to 1 :6, more preferably from 1 :1 to 1 :5, in particular from 1 :1 .5 to 1 :5 with each other.

If the mixture of magnesium phosphonate and calcium phosphonate is also to contain one or both or sodium phosphonate and potassium phosphonate, it is expedient to react phosphonic acid with a mixture of dolomite and a sodium and/or potassium carbonate, hydroxide or oxide.

Thus, in this case, preferably, the mixture of magnesium phosphonate and calcium phosphonate and one or both or sodium phosphonate and potassium phosphonate is obtainable by reacting dolomite and phosphonic acid in the presence of at least one of KOH, KHCO3, K2CO3, K₂O, NaOH, NaHCO₃, Na₂CO₃ and Na₂O.

Preferably, in this reaction the molar ratio of the overall amount of KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2CO3 and Na2O to the overall amount of dolomite is from 20:1 to 1 :20, more preferably from 10:1 to 1 :10, even more preferably from 2:1 to 1 :10, in particular from 2:1 to 1 :5; more particularly from 1 :1 to 1 :5, specifically from 1 :1 to 1 :4.

Preferably, in this reaction the molar ratio of the overall amount of dolomite, KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2CO3 and Na2O to phosphonic acid is of from 1 :1 to 1 :6, more preferably from 1 :1 to 1 :4, in particular from 1 :1 to 1 :3, specifically from 1 :1.5: 1 :3. The invention relates also to the use of a mixture obtainable by reacting dolomite and phosphonic acid for combatting invertebrate pests. The remarks made in context with the application and preparation of mixtures I apply here, too. Preferably, dolomite and phosphonic acid are used in a molar ratio of from 1 :1 to 1 :6, more preferably from 1 :1 to 1 :5, in particular from 1 :1.5 to 1 :5. In a preferred embodiment, the invention relates to the use of a mixture obtainable by reacting dolomite and phosphonic acid in the presence of at least one of KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2COs and Na2O. Preferably, the molar ratio of the overall amount of KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2CO3 and Na2O to the overall amount of dolomite is from 20:1 to 1 :20, more preferably from 10:1 to 1 :10, even more preferably from 2:1 to 1 :10, in particular from 2:1 to 1 :5; more particularly from 1 :1 to 1 :5, specifically from 1 :1 to 1 :4. Preferably, the molar ratio of the overall amount of dolomite, KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2CO3 and Na2O to phosphonic acid is of from 1 :1 to 1 :6, more preferably from 1 :1 to 1 :4, in particular from 1 :1 to 1 :3, specifically from 1 :1.5: 1 :3. Suitable reaction conditions have been described above.

The above-described mixtures have a good pesticidal effect and are thus suitable for controlling animal pests, in particular insects, arachnids, helminths, nematodes or molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities. They are also suitable in the protection of stored products and of materials against pests, and in the hygiene sector. Accordingly, they are suitable for protecting or ridding plants and plant organs from the attack of pests and thus for increasing the harvest yields, or for improving the quality of the harvested material; or for protecting or ridding stored products or materials from the attack of pests. Specifically, they are employed as plant protection agents. They show high plant tolerance and low to no toxicity to vertebrate animals and are tolerated well by the environment.

Therefore, the invention relates to the use of the above-described mixtures for combating invertebrate pests. The invention also relates to a method for combating invertebrate pests, which method comprises treating the invertebrate pests, their habitat, plants, plant propagation material or environment or material which is to be protected or rid from infestation by said pests with a pesticidal ly effective amount of a mixture as described above.

The invention relates moreover to the above-defined mixtures II containing, in addition to component A, a further pesticide B. In mixtures II, the weight ratio of the overall amount of component A (calculated as dry matter) to the overall amount of pesticide B is of from 100:1 to 1 :100, preferably from 50:1 to 1 :10, more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2. Alternatively expressed, the weight ratio of the overall amount of calcium phosphonate, magnesium phosphonate, sodium phosphonate, if present, and potassium phosphonate, if present, to the overall amount of pesticide B is preferably of from 100:1 to 1 :100, more preferably from 50:1 to 1 :10, even more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2 “Calculated as dry matter” means here and in any other instance where this term is used that the given ratios relate to component A in solid form, i.e. containing less than 10% by weight, preferably less than 5% by weight, in particular less than 2% by weight of any solvent (generally water).

Mixtures I and II show in many instances an overadditive, i.e. synergistic, pesticidal effect, meaning that the observed pesticidal effect is higher than would have been expected from the effect of the single components of the mixture. The presence of a synergistic effect can be determined by Colby’s formula (Colby, S. R., "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, pp. 20-22, 1967):

E = x + y - x-y/100

E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b

The invertebrate pests to be combatted are preferably selected from the group consisting of harmful arthropods, molluscs and nematodes and more preferably from harmful insects, arachnids, gastropods and nematodes. The insects are preferably selected from the group consisting of herbivorous sucking insects, herbivorous piercing insects, herbivorous licking insects, herbivorous chewing insects, herbivorous rasping insects, and mixed forms thereof, where herbivorous includes wood-eating. The arachnids are preferably selected from herbivorous mites. The gastropods are preferably selected from slugs and snails and are in particular selected from slugs. Specifically, the invertebrate pests to be combatted are selected from harmful insects and nematodes.

The insects can be of the order of Lepidoptera, Coleoptera, Diptera, Thysanoptera, Hemiptera (examples for suborders: Heteroptera, Homoptera), Hymenoptera, Orthop- tera, Isoptera, Blattaria, Siphonoptera, Thysanura, Dermaptera, Collembola, Phthirap- tera.

Examples for insects from the order Lepidoptera are Heh'othis spp., e.g. H. virescens or H. zea, Pieris spp., e.g. P. brassicae o P. repee, Piuteiia xyiosteiia, Thaumetopoea spp., e.Q. T. processioned, Tineoia spp., e.Q. T. bisselliella, Tortrix spp., e.Q. T. virida- nay.

Examples for insects from the order Coleoptera (beetles) are Aethina spp., e.g. A. tu- mida, Anobium spp., e.g. A. punctatum, Anopiophora spp., e.g. giabripennis, Anthrenus spp., e.g. A. museorum, A. scrophuiariae or A. verbasci, Anthonomus spp., e.g. A. grandis, Attagenus spp., e.g. A. peiiio, Brassicogethes spp., e.g. B. aeneus, Brontispa spp., e.g. B. iongissimi, Carpophilus spp., e.g. C. hemipterus, Corticaria spp., e.g. C. pubescens, Dendroctonus spp., e.g. D. ponderosae, Dermestes spp., e.g. D. iardarius, Diabrotica spp., e.g. D. virgifera, Dienereiia spp. (Cartodere fiium), Gibbium spp., e.g. G. psyiioides, Harmonia spp., e.g. H. axyridis, Hyiurgopinus spp., e.g. H. rufipes, Hyiotrupes spp., e.g. H. bajuius, ips spp., e.g. /. typographus, Lasioderma spp., e.g. L. serricorne, Lathridius spp. (Enicmus minutus), Leptinotarsa spp., e.g. L. decemiineata, Metophtaimus spp., e.g. M. serripenns, Niptus spp., e.g. N. hoioieucus, Oryzaephiius spp., e.g. O. mercator, Ptinus spp., e.g. P. tectus orP. fur, Pyrrhaita spp., e.g. P. iuteoia, Rhizopertha spp., e.g. R. dominica, Rhynchophorus spp., e.g. R. ferruginous, Scoiytinae species, e.g. Scoiytus muitistriatus, Scyphophorus spp., e.g. S. acupunctatus, Sitophilus spp., e.g. S. oryzae orS. granaries, Stegobium spp., e.g. S. paniceum, Tenebrio spp., e.Q. T. moiitor, Triboiium spp., e.Q. T. confusum, Trogoderma spp., e.g. T. angustum or T. granarium, Xestobium spp., e.g. X. rufoviiiosum.

Examples for insects from the order Diptera (flies, mosquitos) are leotes spp., e.g. A. aegypti, A. aibopictus, A. japonicus, A. koreicus, A. sticticus or A. vexans; Anopheles spp., e.g. A. aibimanus, A. arabiensis, A. barber!, A. beiiator, A. crucians, A. cruzii, A. cuiicifacies, A. darting!, A. dirus, A. eartei, A. freeborn!, A. funestus, A. gambiae (Giles 1902), A. introiatus, A. iatens, A. macuiipennis, A. moucheti, A. niii, A. punctipennis, A. quadrimacuiatus, A. stephensi, A. subpictus, A. sundaicus or A. walked, Caiiiphora spp., e.g. C. erythrocephaia or C. vicina, Cecidomyiidae species, Ceratitis spp., e.g. C. capitate, Chloropidae species, Chrysops spp., e.g. C. atianticus, C. discaiis or C. siiacea, Cochiiomyia spp., e.g. C. hominivoraxo C. Maceiiarta, Cuiexspp., e.g. C. pipiens, Cuiiseta spp., e.g. C. annulate, Cuterebra spp., Desineure spp., e.g. D. bressicee or D. oxycoccene, Drosophiie spp., e.g. D. suzukii, Gestrephiius spp., e.g. G. intestineiis, Giossine spp., e.g. G. fuscipes, G. morsitens, G. peipeiis o G. techinoides, Hippoboscidae species, Hypoderme spp., e.g. H. iineete, Leptoconops spp., e.g. L. torrens, Musca spp.,. e.g. M. autumnah's, M. domes tic a or Muscina s tabu! a ns, Oestrus spp., e.g. O. ovis, Phtebotomus spp., e.g. P. argentipes, Psychodidae species, Simuh'um spp., e.g. S. vittatum, Tabanus spp., e.g. T. atratus, T. bovinus, T. Lineota or T. simih's, Tephritidae species.

Examples for insects from the order Thysanoptera (thrips) are Aeotothrips spp., e.g. A. intermedius, Batiothrips spp., e.g. B. dispar, Dendrothrips spp., e.g. D. ornatus, Frankiinieiia spp., e.g. F. occidentaiis, idoiothrips spp., e.g. /. spectrum, Kiadothrips spp., e.g. K. rugosus, Limothrips spp., e.g. L. cereaiium, Retithrips spp., e.g. R. syriacus, Scirothrips spp., e.g. S. dorsalis, Taeniothrips spp., e.g. T. inconsequens, Thrips spp., e.g. T. oryzae, T. paimi, T. tabaci.

Examples for insects from the order Hemiptera (true bugs) are Acrosternum spp., e.g. A. heegeri or A. hiiare, Aieurothrixus s ., e.g. A. f/occosus, Aieyrodes spp., e.g. A. brassicae, Aonidieiia spp., Aphididae species, Aphis spp.,. e.g. A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossuiariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri or A. spiraecoia, Aspidiotus spp., Auiacorthum spp., e.g. A. soiani, Bemisia spp., e.g. B. tabaci, Ceropiastes spp. e.g. C. ceriferus or C. japonic us, Chionaspis spp., e.g. C. teg a lens is, Chrysomphaius spp., e.g. C. a on i di u mor C. dictyospermi, Cimex spp., e.g. C. hemipterus or C. iectuiarius; Coccus spp., e.g. C. hesperidum or C. pseudomagnoiiarum, Cryptomyzus spp., e.g. C. ribis, Dactyiosphaera spp., e.g. D. vitifoiii, Distantieiia spp., e.g. D. theobroma, Dysaphis spp., e.g. D. piantaginea, D. pyri orD. radicola, Dysdercus spp., Empoasca spp., e.g. E. vitis, Eriosoma , e.g. E. ianigerum, Erythroneura spp., Euchistus spp., Eurygaster spp., Gascardia spp., Laodeiphax spp., Lecanium spp., e.g. L. comi, Lepidosaphes spp., Leptocorisa spp., Lygus spp., Macrosiphum, spp., e.g. M. rosae, Myzus spp., e.g. M. persicae, Nephotettix spp., e.g. N. incticeps, Nezara spp., Niiaparvata spp., e.g. N. iugens, Paratoria spp., Pemphigus spp., Piesma spp., Pianococcus spp., Pseudauiacaspis spp., Pseudococcus spp., Psyiias yp., e.g. P. mail or P. pyri, Puivinaria spp., e.g. P. aethiopica, Quadraspidiotus spp., Reduvius spp., e.g. R. senilis, Rhodnius spp., Rhopaiosiphum spp., Sahibergeiia singuiaris, Saissetias ., e.g. S. coffeae, Scaphoideus spp., Schizaphis spp., Scotinophara spp., Sitobion spp., Triaieurodes spp., 0.0,. T. vaporariorum, Triatoma spp., Trioza spp., e.g. T. erytreae, Unaspis spp., e.g. U. Ci tri.

Examples for insects from the order Hymenoptera (ants, bees, wasps, sawflies) are Acromyrmex spp., Atta spp., C eph us spp., Diprion spp., Diprion idae species, Giipinia spp., e.g. G. poiytoma, Hopiocampa spp., Lasius spp., Monomorium spp., e.g. M. pharaonis, Neodiprion spp., Soienopsis spp., Vespa spp. Examples for insects from the order Orthoptera (crickets, grasshoppers, locusts) are Gryllotalpa spp., Leucophaea spp., e.g. L. maderae, Locusta spp., Periplaneta spp., Schistocerca spp.

Examples for insects from the order Isoptera (termites) are Coptotermes spp., e.g. C. formosanus, Leucotermes flavipes, Matotermes spp., Neotermes spp., Reticuiitermes spp-

Examples for insects from the order Blattaria (cockroaches) are Blattaspp., e.g. B. orientalis orB. lateralis, Blattella spp., e.g. B. asahinae orB. germanica, Eurycotis spp., e.g. E. f/oridana, Leucophaea spp., e.g. L. maderae, Panchlora spp., e.g. P. nivea, Parcoblatta spp., e.g. P. pennsylvanica, Periplaneta spp., e.g. P. americana, P. austra/asiae, P. brunnea, P. fuligginosao P. japonica; Pycnosce/us spp., e.g. P. surinamensis, Supella spp., e.g. S. longipalpa.

Examples for insects from the order Siphonoptera (fleas) are Ceratophyllus spp. and Xenopsylla spp., e.g. X. cheopis.

Examples for insects from the order Thysanura (silverfish, firebrat) are Lepisma spp., e.g. L. saccharina.

Examples for insects from the order Dermaptera (earwigs) are Forficu/a spp., e.g. F. auricularia.

Examples for insects from the order Collembola are Onychiurus spp., e.g. O. armatus.

Examples for insects from the order Phthiraptera (lice) are Dama/inia spp., Pedicu/us spp., e.g. Pedicu/us hum an us capitis, Pedicu/us humanus corporis or Pedicu/us humanus humanus, Pthirus spp., e.g. P. pubis, Haematopinus spp., e.g. H. eurysternus or H. suis Linognathus spp., e.g. L. vituii; Bovicoia spp., e.g. B. bovis, Menopon spp., e.g. M. gaiiinae, Menacanthus spp., e.g. M. stramineus, Soienopotes spp., e.g. S. capiiiatus, Trichodectes spp.

The arachnids can be of the order of Acari. Examples are Acarus spp., e.g. A. siro, Aceria spp., e.g. A. sheidoni, Acuius spp., e.g. A. schiechtendaii, Ambiyomma spp., Argas spp., Boophiius spp., Brevipaipus spp., Bryobia spp., e.g. B. praetiosa, Caiipitrimerus spp., Cecidophyopsis spp., e.g. C. ribis, Chorioptes spp., Demodex species, Dermanyssus spp., e.g. D. ga/hhae, Eotetranychus spp., e.g. E. carpinio E. tii- iarium, Eriophyes spp., Hyalomma spp., Ixodes spp., Neotrombicula spp., e.g. N. au- tumnah's, OUgonychus spp., e.g. O. pratensis, Ornithodoros spp., Panonychus spp., e.g. P. citri or P. ulmi, Phyllocoptruta oleivora, Polyphagotarsonemus spp., e.g. P. la- tus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tar- son emus spp., Tetranychus spp., e.g. T. cinnabarinus or T. urticae , Trombicuhdae species, Varroaspp., e.g. I/, destructor. Herbivoric mites are e.g. Acarus spp., e.g. A. siro, Aceria spp., e.g. A. shetdoni, Acutus spp., e.g. A. schtechtendati, Brevipatpus spp., Bryobia spp., e.g. B. praetiosa, Catipitrimerus spp., Cecidophyopsis spp., e.g. C. ribis, Eotetranychus spp., e.g. E. carpinio E. tih'arium, Eriophyes spp., OUgonychus spp., e.g. O. pratensis, Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus spp., e.g. P. iatus, Rhizoglyphus spp., Tarsonemus spp., Tetranychus spp., e.g. T. cinnabarinus or 7". urticae.

Examples of gastropods are Arion spp., e.g. A. vulgaris, Biomphaiaria spp., Buiinus spp., Deroceras spp., e.g. D. reticuiatum, Gaibaspp., Lymnaea spp., Oncomeiania spp., Pomacea spp., e.g. P. canal iciata, Succinea spp..

Examples of nematodes are Giobodera spp., Heterodera spp., e.g. Heterodera schachtii; Meioidogyne spp., Pratyienchus spp. (lesion nematodes , Rhodophoius spp., Tyienchuius spp..

In a particular embodiment, the invertebrate pests to be combated are insects; specifically insects from the order Hemiptera.

In another particular embodiment, the invertebrate pests to be combated are nematodes, e.g. Heterodera spp.

In a preferred embodiment, the pesticidal use and method of the invention serve for combatting harmful invertebrate pests in or on plants, plant propagation material and/or soil wherein the plants grow or are to grow.

"Plant propagation material" refers to all generative parts of plants from which a complete plant can grow, such as seeds, grains, fruits, tubers, the rhizome, spores, cuttings or meristem tissue. Preferably, it refers to seeds.

The term "soil" as presently used is not restricted to soil as such (i.e. the material forming the pedosphere), be it present in the field, in a pot or border, but encompasses any suitable growth medium or growth substrate in which plants can grow, thus also artificial media. Preferably, however, it means soil in the proper sense. All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants include plants obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including transgenic plants. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds and also roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, habitat or storage space by the customary treatment methods, for example by spraying, evaporation, fogging, scattering, immersion, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats. Seed can be attacked during storage and after the seed is introduced into the soil, and during and immediately after germination of the plants. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive and even minor damage can lead to the death of the whole plant. Protecting the seed and the germinating plant is therefore of the same interest as protecting the overground plant parts.

The mixtures of the invention or to be used according to the present invention can be employed for pest control in cereals, such as wheat (inclusive spelt, einkorn, emmer, kamut, durum and triticale), rye, barley, rice, wild rice, maize (corn), millet, sorghum, teff, fonio and oats; in pseudocereals, in fruit, for example pome, stone and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries and blackberries, currant; in leguminous plants, such as beans, lentils, peas or soya; in oil-bearing crops, such as oilseed rape, mustard, poppy, olive, sunflower, coconut, castor, cacao or groundnuts; in cucurbits, such as pumpkins, cucumbers, zucchini, or melons; in fibre plants, such as cotton, flax, hemp or jute; in citrus fruits, such as oranges, lemons, grapefruits or mandarins; in vegetables, such as spinach, lettuce, asparagus, cabbage varieties, carrots, onions, bell pepper, tomatoes, potatoes, sweet potatoes, turnip, parsnip, radish, beetroot, sugar beets, onion, garlic, leek or capsicum; in lauraceous plants, such as avocado, cinnamon or camphor; or in tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, natural rubber plants, trees in general (wild growing, in forestry, in plantations, in orchards, in gardens, on streets), shrubs, grass, lawn, turf, fodder grass or ornamentals.

The plants are preferably treated in such a way that the plant or plant parts thereof are contacted with the active compounds. As explained above, the term "mixture" in this context is not limited to a physical mixture. Thus, in case that mixtures I or II are used, the active components (magnesium phosphonate and calcium phosphonate in mixtures I; sodium and/or potassium phosphonates, if present in mixtures I; component A and pesticide B in mixtures I or II, where the components of component A can also be used separately) can be applied to the plant or to the plant parts in form of a physical mixture or separately. In the case of separate application, the active components can be applied simultaneously or successively, though, in the latter case, the individual components should be applied within a short time interval, preferably within a time interval of a few seconds or a few minutes, for example 1 , 2 or 3 minutes, up to 1 day. At least in case of mixtures I, preference is however given to combined application using a ready-to-use formulation which comprises all phosphonate salts (i.e. at least mixtures I are preferably used as a physical mixture).

These remarks apply analogously to the treatment of seeds or soil.

The mixtures I and II as well as the single phosphonates or the pesticides B can be formulated into a composition, including in addition a suitable inert liquid carrier (diluent) or solid carrier and, optionally, a surface active agent. Surface active agents are chemicals which are able to modify the properties of an interface (for example, liquid/solid, I iquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). The formulated compositions (both solid and liquid formulations) comprise typically 1 to 99% by weight, e.g. 1 to 99% by weight, preferably 10 to 80% 1 to 99% by weight, of the active compound(s). The formulated compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EC)), micro-emulsions (ME), suspension concentrates (SC) etc.. The formulation type chosen will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the active compounds.

Suitable carriers depend on the formulation used. Examples for solid carriers include mineral earths, ground synthetic materials, solid fertilizers, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal, nutshell meal, cellulose powders. Examples for liquid carriers include water, organic solvents and oils of vegetable or animal origin.

Surface active agents can act as wetting agents, dispersing agents, emulsifying agents, suspending agents or spreaders. They may be of the cationic, anionic, amphoteric or non-ionic type.

Suitable surface active agents of the cationic type include quaternary ammonium compounds (for example cetyltri methyl ammonium bromide), imidazolines and amine salts.

Suitable anionic surface active agents include alkali metals salts of fatty acids (e.g. soaps, such as potassium soap), salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate, mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulfonates, and the alkali metal, alkaline earth metal, ammonium and amine salts of naphthalenesulfonic acids), ether sulfates, alcohol ether sulfates (for example sodium laureth-3-sulfate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately diesters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates, taurates and lignosulfonates.

Suitable surface active agents of the amphoteric type include betaines, propionates and glycinates.

Suitable surface active agents of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, lecithins or organosilicons, such as the Silwet® brands. Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite). In a particular embodiment, alkali metals salts of fatty acids are used as surface active agents. Specifically, potassium soap is used. Potassium soap is typically obtained by hydrolyzing natural fats and/or oils with KOH. Uniform products can be obtained by neutralizing a specific fatty acid, e.g. oleic, palmitic or stearic acid, with KOH. For the purposes of the present invention, all types of potassium soap are suitable.

Before application to the target (pest, plant, soil, material etc.), the above-listed liquid formulations are generally diluted with water. The solid formulations can also be dispersed in water, or are alternatively used in solid form.

The phosphonates or mixtures I or component A of mixtures II can be applied as liquid formulations, in particular as aqueous dispersions. The phosphonic acid salts are either water-soluble and can thus be applied, for example, as aqueous solutions, or are not or not completely water-soluble and can for example be applied as an aqueous suspension or colloid. The aqueous suspensions to be eventually applied are for example obtained from a suspension concentrate (SC), wettable powder (WP) or water-dispersible granulate (WG) which is diluted with water to the desired concentration. Alternatively, the phosphonic acid salts or mixtures I or component A of mixtures II can be applied in solid form, such as a dust, powder or granules, or also in form of special formulations like seed coatings and pellets. In this case the formulation serves either for protecting seeds from pest attack or serves as a bait.

Aqueous ready-to-use formulation contain the phosphonates of mixtures I or II in an overall amount of preferably from 0.005 to 50 g/l, more preferably from 0.01 to 30 g/l, in particular from 0.01 to 20 g/l, more particularly from 0.05 to 10 g/l, even more particularly from 0.1 to 5 g/l and specifically from 0.1 to 1 g/l.

Suitable application forms of pesticides B depend on the individual agent and can be determined by the skilled person. Given that pesticides B are known in the art and are generally also commercially available, the suitable application forms are principally known to the skilled person.

If mixtures I or II are to be applied as physical mixtures, the mixtures I or II are generally applied as liquid formulations, in particular as aqueous formulations, or in solid form, e.g. in dust or powder form or in form of granules. The mixtures can also be applied in form of special formulations like seed coatings and pellets. In this case, the formulation serves either for protecting seeds from pest attack or serves as a bait. The treatment of the plants or parts thereof or of the seeds or soil in which the plant grow or is to grow can be both protective and curative, i.e. before or after an infestation with invertebrate pests. It is preferably carried out as close in time as possible to the infestation event, i.e. before or after the infestation at a point in time which is as close as possible to the infestation. More preferably, it is carried out as curative treatment, i.e. after an infestation with invertebrate pests has taken place.

The timing of the application, the number of applications and the application rates employed in each case have to be adapted to the prevailing conditions and have to be determined for each individual case by a person skilled in the art.

For instance, the overall application rate for a protective treatment via foliar application is generally in the range of from 0.01 to 100 kg/ha of all phosphonates of mixtures I or II, preferably from 0.1 to 50 kg/ha, more preferably from 0.1 to 20 kg/ha, in particular from 1 to 15 kg/ha and specifically from 2 to 10 kg/ha. The optimum application rates depend inter alia on the plant to be treated, on weather conditions (rainy conditions, for instance, generally making higher rates necessary), on the intensity of the infestation, on the infesting pest and on whether a protective or curative treatment is carried out, and can be determined for the individual case by the skilled person.

The optimum application rates of pesticides B depend on the individual pesticides and of course also inter alia on the plant to be treated, on weather conditions, on the intensity of the infestation and on the infesting pest, and can be in the range of from 0.1 to 4000 g/ha, desirably from 1 to 2000 g/ha, more desirably from 5 to 1000 g/ha, e.g. 10 to 600 g/ha. In the case of botanical essence (B.33) and Diatomaceous earth or kaolin (B.35), suitable application rates might however be distinctly higher, e.g. from 0.01 to 100 kg/ha or from 0.1 to 50 kg/ha or from 0.1 to 20 kg/ha or from 1 to 15 kg/ha or from 2 to 10 kg/ha.

If the present mixtures I or II or the single phosphonates are used as an aqueous formulation in foliar application, the aqueous formulation may contain an adjuvant facilitating the penetration of plant cuticles, such as a wetting agent. The amount of wetting agent depends both on the type of agent and the plant target surface and is typically in the range from 0.001 to 1% by weight, in particular from 0.01 to 0.5% by weight, based on the total weight of the ready-to-use formulation. Wetting agents have been described above. They can be of anionic or nonionic nature and are, for example, soaps, e.g. soft soap (potassium soap, i.e. potassium salt of fatty acids); naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, fatty alcohol ethoxylates, ethoxylated alkylphenols, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters or organosilicons, such as the Silwet® brands.

The above-described mixtures I or II are not limited to act as a pesticide on plants, but have a general pesticidal action and can thus also be used for protecting materials different from plants, plant propagation material and soil in which the plants grow or are to grow, such as, for example, inanimate material, from pesticidal attack, or for combatting invertebrate pests on materials different from plants, plant propagation material or soil in which the plants live or are to grow, such as, for example, inanimate material. Thus, the present mixtures can also be used as a preservative and/or in the control of invertebrate pests in or on inanimate material.

Inanimate material to be treated according to the invention is for example foods. Another example for inanimate material is construction materials, such as in particular timber or polymeric materials, wooden materials in general, such as furniture, fences, doors or particle boards, leather, fibers or clothing. For controlling infectious diseases transmitted by invertebrate pests (e.g. malaria, dengue fever, yellow fever, leishmanio- sis, bilharziosis), the present mixtures can moreover be used to treat surfaces of huts, houses, tents, industrial or commercial facilities, or buildings for livestock, and to im- pregnate/spray curtains, tents, clothing items, bed nets, tsetse-fly traps or the like. The present mixtures are moreover suitable for the protection of stored products, and also in the protection of domestic animals and productive livestock against pests of the type mentioned.

The mixtures I and II are effective through both contact (e.g. via plants, plant parts, plant propagation material, soil, animal surfaces, surfaces in dwellings, tents, facilites or buildings for livestock, such as glass, wall, furniture, carpets, curtains, bed nets, fly traps, clothing, carpet), and ingestion (e.g. via plants, plant parts, plant propagation material, harvested crops, wood, fibers, clothing or bait).

Suitable baits can take any known form (liquid, solid, pasty, jellylike etc.), as long as they are sufficiently attractive to incite the pest to be combated to ingest it. The bait’s appeal can be induced or enhanced by feeding stimulants, such as sugar, glucose, fructose, starch, cellulose, bran, honey, fish meal, fats, oil, fruits, vegetables, crops, etc., or by sex pheromones.

A specific example for the use as bait is the use in a bait for molluscs, in particular for gastropods, such as snails and slugs. The invention relates moreover to the use of component A as defined above (i.e. mixture comprising magnesium phosphonate and calcium phosphonate) as a synergist for a pesticide B (which is as defined in context with mixture I or with mixtures II). “Synergist” in this context means that component A enhances the pesticidal effect of a compound B. The effect is overadditively enhanced, meaning that the observed effect is larger than what would have been expected from the effects of components A and B when used individually (e.g. as calculated by Colby’s formula). This effect allows the use of pesticides B in lower concentration. While many pesticides B can be environmentally problematic, component A shows high plant tolerance and low to no toxicity to vertebrate animals and is tolerated well by the environment. The combination of components A and B thus allows the preparation of a better tolerated and less toxic composition without disadvantages for the pesticidal activity.

Mixtures I containing calcium phosphonate and magnesium phosphonate are surprisingly effective against invertebrate pests and can be used for the protective and curative treatment of plants as well as for the treatment of arbitrary, also inanimate, substrates. Mixtures comprising at least one primary magnesium and/or calcium phosphonate and at least one secondary magnesium and/or calcium phosphonate as well as mixtures I additionally comprising at least one of sodium and potassium phosphonate combine a long-lasting with an imminent action. Without wishing to be bound by theory, it is assumed that the long-lasting effect is at least partially due to the low water solubility of secondary calcium and magnesium phosphonates, thus releasing the active agent only slowly. Mixtures I show high plant tolerance and low to no toxicity to vertebrate animals and are tolerated well by the environment.

The invention is now illustrated by the following examples.

Examples

A. Synthetic examples

Dolomite powder (both non-calcinated and fully calcinated) was obtained from Dolo- mitwerk Jettenberg, Germany. Phosphonic acid was obtained from ICL-IP Bitterfeld- Wolfen, Germany. The water used was demineralized water. The silicone defoaming agent used in example B.4 is the product BUZ Defoam G478 from Buzil-Werk Wagner Gmbh & Co. KG in Memmingen, Germany.

Example 1 : Synthesis of magnesium/calcium/sodium phosphonate 1050 g of phosphonic acid (in solid form; 12.8 mol), 525 g of non-calcinated dolomite (2.85 mol) with a particle size of ca. 20 pm and 250 g of Na2COs (2.36 mol) were premixed in a stirrer and the reaction was started by addition of 100 ml of water. When the viscosity increased, more water was added to keep the mass stirrable until gas evolution stopped and the conversion into phosphonates was finished, resulting in a suspensions with a density of about 1 .4 kg/l.

Example 2: Synthesis of magnesium/calcium/potassium phosphonate

The process of example 1 was repeated, using however 325 g of K2CO3 (2.36 mol) instead of Na2COs.

Example 3: Synthesis of magnesium/calcium phosphonate

0.1 mol of phosphonic acid in solid form was added to 0.05 mol of fully calcinated dolomite (CaMgC>2; purity >95%) with a particle size of ca. 63 pm. The reaction mixture was premixed in a stirrer, the reaction was started by addition of 30 ml of water and the mixture was heated to 60°C for 1 h. When the viscosity increased, another 30 ml of water was added to keep the mass stirrable. After one day at room temperature the reaction product was tested for its biological activity.

Example 4: Synthesis of magnesium phosphonate (for comparison)

The procedure of example 3 was repeated, using however 0.1 mol of MgO (from Merck chemicals, fine powder; analytical grade) instead of fully calcinated dolomite.

Example 5: Synthesis of calcium phosphonate (for comparison)

The procedure of example 3 was repeated, using however 0.1 mol of CaO (from Merck chemicals, fine powder; analytical grade) instead of fully calcinated dolomite.

Example 6: Synthesis of magnesium/calcium/potassium phosphonate

100 g (1 mol) of KHCO3 were thoroughly mixed with 600 g (3.26 mol) of non-calcinated dolomite (dolomite in the proper sense). 267 g of this premix (containing thus 0.38 mol of KHCO3 and 1 .24 mol of dolomite) were mixed with 328 g (4 mol) of H3PO3 (in solid form). 100 ml of water were added and the mixture was stirred at 40°C until reaction started, indicated by strong foam formation (due to evolution of CO2). The reaction mix- ture was transferred to an oven and heated to 80°C for ca. 30 min. To remove remaining water from the reaction mixture, which had turned into a solid mass, the mass was disintegrated and heated to 100°C for another 30 min. After cooling, the resulting dry mass was comminuted.

B. Biological examples

B.1 Rose Aphid Macrosiphum rosae) on rose (field test with different rose varieties in garden)

The suspension of example 2 was diluted to a final concentration of the phosphonates of 5 g/l using water containing 0.1 % (w/w) of soft soap (potassium soap) to improve wetting of the surface (leaf and/or stemlet) of rose plants which were naturally and densely infested with aphids. As a control, other twigs of the same plant with buds comparably infected by aphids were marked and sprayed with 0.1% (w/w) of soft soap in water only. All applications were done with small precision pump spraying units. Each experimental set contained at least 10 replicates resp. individual rose buds. The total set contained 21 rose plants of different varieties. Relative coverages of aphids (control = 100%) were visually assessed directly after application, and after 1 , 2 and 7 days. The results are compiled in table B.1 .

Table B.1

* with the phosphonates from example 2

B.2 Aphid (Aphis sambuci) on elder

In late spring and early summer the upper part of young elder shoots or stemlets of elder flowers are frequently covered completely by populations of Aphis sambuci, associated with ants who feed on the honeydew produced by the aphids. The naturally infested plants (one culture variety of Sambucus nigra in garden and 6 wild growing elders) were treated as described in example B.1 . The results are compiled in table B.2. Table B.2

* with the phosphonates from example 2

B.3 Aphid Dysaphis plantaginea) on apple (varieties “Elstar” and “Rubinette”)

Dysaphis plantaginea \ca\\ forms less dense populations, however causes severe plant damage resulting in leaf deformation and rolling. Visual estimation of relative area coverage is thus difficult. Instead, one week after treatment, deformed plant parts were checked for individual aphids responding on touch by a fine paintbrush.

Each 10 twig tips of two apple tree varieties (Elstar and Rubinette), showing significant leaf deformation by natural infestation with Dysaphis plantaginea were treated either with the suspension of example 1 diluted with water containing 0.1% (w/w) of soft soap (potassium soap) to a final concentration of the phosphonates of 5 g/l, or, as a control, with water containing 0.1 % (w/w) of soft soap, with special care that the abaxial leaf sites were hit by spray.

Results:

In both apple varieties, one week after treatment more than 50% of the aphids of the controls moved when touched. On plant parts treated with the phosphonates from example 1 , less aphids were found, and almost none of the remaining aphids showed reaction on touching.

B.4 Aphid (Cryptomyzus ribis) on currant

This aphis species typically causes severe deformation of youngest leaves at the shoot tips, encasing and such protecting the aphids to be hit directly by spray. Instead of direct evaluation of the effect on aphids the further development of shoot tips and regular growth of newly formed leaves were rated 3 weeks after treatment. Each six currant shrubs were either treated by motor sprayer with the suspension of example 1 diluted to a final concentration of the phosphonates of 5 g/l using water containing 0.02% (w/w) of silicone defoaming agent to improve plant wetting, or, as a control, with water containing 0.02% (w/w) of silicone defoaming agent.

Results:

Comparing the development of new leaves following the treatment resulted in a striking difference: Each shrub treated with the phosphonates from example 1 showed normal development of shoot tips without leaf deformation, whereas newly formed leaves of the control plants still had the typical symptoms for infestation by Cryptomyzus ribis.

B.5 Leaf sucker (Psyiia spp.) on pear trees (variety “Gute Luise”)

The trees to be treated were old pear trees (about 60 years old) from a former orchard, all suffering from severe infestation with leaf suckers. Three whole trees were treated end of May 2019 and mid-June 2019 with a motor sprayer using the suspension obtained in example 2 diluted with water to a concentration of the phosphonates of 5 g/l . Two weeks and four weeks after the second treatment the trees were assessed for active leaf suckers both visually and by an “indirect acoustic method”: Typically pear leaf suckers attract many wasps feeding on the honeydew, resulting in a humming background noise.

Results:

Two weeks after the second treatment the difference between non treated controls and pear trees treated with the suspension of example 2 became very clear, still holding on after 4 weeks: All untreated controls were infested heavily by Psylla leaf suckers, already associated with necrotic lesions on leaves and high abundance of wasps feeding on the honeydew of the pests. In contrast thereto, the three trees treated with the suspension of example 2 were almost free of leaf suckers, with healthy leaves and without abundance of insects feeding on honeydew.

B.6 Leaf sucker Psylla spp.) on fig tree (Homotoma ficus)

On the trial site, on the leaves of Homotoma ficus heavily infested, the nymphs of leaf sucker formed an essentially dense line of nymphs directly sucking at the major leaf veins. Four whole trees were sprayed twice at an interval of one week with the suspension of example 1 diluted with water to a concentration of the phosphonates of 5 g/l and visually assessed for remaining suckers one week after the second application.

Results: The result was striking: All untreated controls were infested heavily by Psylla leaf suckers, also developing figs and nearby shrubs, whereas the treated trees were completely free of leaf suckers.

B.7 Sugarbeet cyst nematode (Heterodera schachtii) on sugarbeet

16 pots were filled with each 500 g of soil, preinfested with 5 cysts (full with eggs) of sugarbeet cycst nematodes. Two days later, half of the pots were treated with each 25 ml of water for negative control, and the other half was treated with each 500 mg of calcium-magnesium phosphonate as obtained in example 6 dispersed in 25 ml of water. To make sure that the soil didn’t contain excess moisture, no further water was applied for two days after that treatments. Two sugar beet seeds were then sown per pot, retaining the most vigorous plant after one week for further development. 3 weeks after planting, all pots were inoculated with an additional 200 larvae of sugarbeet cycst nematodes in growth stage J2 to boost the infection. Examination of roots with counting of cysts was done six weeks after planting (WAP). The results (average number of nematode cysts per pot and standard deviation) are compiled in the table below.

As the results show, the soil treatment with Ca/Mg phosphonate results in a significant reduction of the number of sugarbeet cycst nematodes.

B.8 English grain aphid (Sitobion avenae) on wheat - synergistic effect

Cultures of aphids (Sitobion avenae) on wheat in bankerplants were supplied by re- natur GmbH, 24601 Stolpe Germany and maintained in small illuminated cabinets at 20°C with weekly transfer onto young winter wheat plantlets (1^st leaf developed).

Seeds of winter wheat were soaked in water for 12 h before placing each 50 seeds in 7x7cm pots containing water-saturated potting soil for germination and growing.

When the first leaves were fully developed (about 10 days after seeding), the plantlets were treated with either the aqueous suspensions of example 3 (Ca-Mg phosphonate), or of example 4 (Mg phosphonate) or of example 5 (Ca phosphonate) by application with small aerosol pumping sprayers for all-over wetting just before run-off. A part of the pots remained untreated (control). The pots were inoculated with each about 200 aphids by placing infested pieces of leaves from aphid culture between the wheat plantlets. The pots were incubated in small growing cabinets at 20°C, keeping wet by watering from the bottom. One day after treatment (DAT) and then six days after treatment the numbers of aphids feeding on the test plants were estimated and averaged.

For each treatment 3 pots (3 x 50 plants) were evaluated for efficiency of control, with the means of numbers of aphids on non-treated plants representing 0% control and no aphids on the treated leaves representing 100% control.

Synergism was calculated according to Colby’s formula:

E = x + y - x-y/100

E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b

The results are compiled in the table below.

* according to Colby

As can be seen from the results, the mixture used according to the invention has a synergistic effect.

Claims

45 We claim:

1 . The use of a mixture comprising magnesium phosphonate and calcium phospho- nate for combating invertebrate pests, where the mixture optionally also comprises sodium phosphonate and/or potassium phosphonate.

2. The use as claimed in claim 1 , where the molar ratio of calcium phosphonate to magnesium phosphonate is of from 10:1 to 1 :10, preferably from 5:1 to 1 :5.

3. The use as claimed in claim 2, where the molar ratio of calcium phosphonate to magnesium phosphonate is of from 2:1 to 1 :2, preferably from 1.5:1 to 1 :1.5, specifically approximately 1 :1.

4. The use as claimed in any of the preceding claims, where in case that the mixture also comprises sodium phosphonate and/or potassium phosphonate, the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 20:1 to 1 :20, preferably from 10:1 to 1 :10.

5. The use as claimed in claim 4, where the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 2:1 to 1 :10, preferably from 2:1 to 1 :5.

6. The use as claimed in claim 5, where the molar ratio of the overall amount of sodium phosphonate and potassium phosphonate to the overall amount of magnesium phosphonate and calcium phosphonate is from 1 :1 to 1 :5, preferably from 1 :1 to 1 :4.

7. The use as claimed in any of the preceding claims, where the mixture of magnesium phosphonate and calcium phosphonate comprises at least one of primary magnesium phosphonate and primary calcium phosphonate and at least one of secondary magnesium phosphonate and secondary calcium phosphonate.

8. The use as claimed in any of the preceding claims, where the mixture of magnesium phosphonate and calcium phosphonate is obtainable by reacting dolomite with phosphonic acid. 46

9. The use as claimed in claim 8, where dolomite is selected from dolomite in the proper sense, dolomite in partially calcinated form, dolomite in fully calcinated form and mixtures thereof.

10. The use as claimed in any of claims 8 and 9, where dolomite and phosphonic acid are reacted in a molar ratio of from 1 :1 to 1 :6, preferably from 1 :1 to 1 :5, more preferably from 1 :1 .5 to 1 :5.

11 . The use as claimed in any of claims 8 to 10, where the mixture of magnesium phosphonate and calcium phosphonate is obtainable by reacting dolomite and phosphonic acid in the presence of at least one of KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2COs and Na2O.

12. The use as claimed in claim 11 , where the molar ratio of the overall amount of KOH, KHCO3, K2CO3, K₂O, NaOH, NaHCO₃, Na₂CO₃ and Na₂O to the overall amount of dolomite is from 20:1 to 1 :20, preferably from 10:1 to 1 :10, more preferably from 2:1 to 1 :10, in particular from 2:1 to 1 :5; more particularly from 1 :1 to 1 :5, specifically from 1 :1 to 1 :4.

13. The use as claimed in any of claims 11 to 12, where the molar ratio of the overall amount of dolomite, KOH, KHCO3, K2CO3, K2O, NaOH, NaHCOs, Na2CO3 and Na2O to phosphonic acid is of from 1 :1 to 1 :6, preferably from 1 :1 to 1 :3.

14. The use as claimed in any of the preceding claims, of a composition comprising

A. as component A the mixture comprising magnesium phosphonate and calcium phosphonate as defined in any of the preceding claims; and

B. as component B at least one further pesticide B, where the pesticide B is selected from the group consisting of:

B.1 acetylcholine esterase inhibitors selected from the class of carbamates which are in turn selected from the group consisting of alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, iso- procarb, methiocarb, methomyl, metolcarb, oxamyl, primicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or selected from the class of organophosphates which are in turn selected from the group consisting of acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyr- ifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos disul- 47 foton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthi- on, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecar- bam, methamidaphos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxymethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimi- phos-methyl, profenofos , propetamphos, prothiofos, pyraclofos, pyri- daphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetra- chlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion;

B.2 GABA-gated chloride channel blockers selected from the class of cyclodiene organochlorines which are in turn selected from the group consisting of chlordane and endosulfan; or selected from the class of phenylpyra- zoles which are in turn selected from the group consisting of acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole and vaniliprole;

B.3 sodium channel modulators selected from the class of pyrethroids or pyre- thrins which are in turn selected from the group consisting of acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, beta-cyfluthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, th eta-cy permethrin, zeta-cypermethrin, cyphenothrin [(1 R)-trans- isomers], deltamethrin, em- penthrin [(EZ)- (1 R)- isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, kadathrin, metofluthrin, permethrin, phenothrin [(1 R)-trans- isomer], prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetrame- thrin [(1 R)- isomer], tralomethrin and transfl uthrin; or selected from the group consistng of DDT and methoxychlor;

B.4 nicotinic acetylcholine receptor (nAChR) competitive modulators selected from the class of neonicotinoids which are in turn selected from the group consisting of acetamiprid, clothianidin, dinotefuran, imidacloprid, niten- pyram, thiacloprid and thiamethoxam; or selected from the group consisting of nicotine, sulfoxaflor, flupyradifurone and triflumezopyrim;

B.5 nicotinic acetylcholine receptor (nAChR) allosteric modulators - Site I selected from the class of spinosyns which are in turn selected from the group consisting of spinetoram and spinosad;

B.6 glutamate-gated chloride channel (GluCI) allosteric modulators selected from the group consisting of abamectin, emamectin benzoate, lepimectin and milbemectin; B.7 juvenile hormone mimics selected from the group consisting of hydroprene, kinoprene, methoprene, fenoxycarb and pyriproxyfen;

B.8 miscellaneous non-specific (multi-site) inhibitors selected from the group consisting of methyl bromide and other alkyl halides, chloropicrin, cryolite, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium borate, sodium metaborate, tartar emetic, dazomet and metam;

B.9 chordotonal organ TRPV channel modulators selected from the group consisting of pymetrozine and pyrifluquinazon;

B.10 mite growth inhibitors selected from the group consisting of clofentezine, di- flovidazin, hexythiazox and etoxazole;

B.11 microbial disruptors of insect midgut membranes selected from the group consisting of Bacillus thuringiensis and the insecticidal proteins they produce and Bacillus sphaericus;

B.12 inhibitors of mitochondrial ATP synthase selected from the group consisting of diafenthiuron, organotin miticides selected from the group consisting of azocyclotin, cyhexatin and fenbutatin oxide; propargite and tetradifon;

B.13 uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from the group consisting of chlorfenapyr, DNOC and sulflu- ramid;

B.14 nicotinic acetylcholine receptor (nAChR) channel blockers selected from the group consisting of bensultap, cartap hydrochloride, thiocyclam and thi- osultap-sodium;

B.15 inhibitors of chitin biosynthesis, type 0 selected from the group consisting of bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hex- aflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and tri- flumuron;

B.16 the inhibitors of chitin biosynthesis, type 1 buprofezin;

B.17 the moulting disruptor cyromazine;

B.18 ecdysone receptor agonists selected from the group consisting of chromaf- enozide, halofenozide, methoxyfenozide and tebufenozide;

B.19 the octopamine receptor agonist amitraz;

B.20 mitochondrial complex III electron transport inhibitors selected from the group consisting of hydramethylnon, acequinocyl, fluacrypyrim and bifena- zate;

B.21 mitochondrial complex I electron transport inhibitors selected from the group consisting of fenazaquin, fen pyroxi mate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad and rotenone;

B.22 voltage-dependent sodium channel blockers selected from the group consisting of indoxacarb and metaflumizone; B.23 inhibitors of acetyl CoA carboxylase selected from the group consisting of spirodiclofen, spiromesifen, spiropidion and spirotetramat;

B.24 mitochondrial complex IV electron transport inhibitors selected from the group consisting of aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, calcium cyanide, potassium cyanide and sodium cyanide;

B.25 mitochondrial complex II electron transport inhibitors selected from the group consisting of cyenopyrafen and pyflubumide;

B.26 ryanodine receptor modulators selected from the group consisting of chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole;

B.27 the chordotonal organ modulator of undefined target site flonicamide;

B.28 the GABA-gated chloride channel allosteric modulator fluxametamide;

B.29 compounds of unknown or uncertain mode of action selected from the group consisting of azadirachtin, benzoximate, bromopropylate, chinome- thionat, dicofol, pyridalyl, sulfur and lime sulfur;

B.30 Baculoviruses selected from the group consisting of Cydia pomonella GV, Thaumatotibia leucotreta GV, Anticarsia gemmatalis MNPV and Helicover- pa armigera NPV;

B.31 the nicotinic acetylcholine receptor (nAChR) allosteric modulator - site II GS-omega/kappa HXTX-Hv1a peptide;

B.32 bacterial agents (non-Bt) of unknown or uncertain mode of action selected from the group consisting of Burkholderia spp and Wolbachie pipientis (Zap);

B.33 botanical essence including synthetic, extracts and unrefined oils with unknown or uncertain mode of action selected from the group consisting of Chenopodium ambrosioides near ambrosioides extract, fatty acid monoesters with glycerol or propanediol and Neem oil;

B.34 fungal agents of unknown or uncertain mode of action selected from the group consisting of Beauveria bassiana strains, Metarhizium anisopliae strain F52 and Paecilomyces fumosoroseus Apopka strain 97; and

B.35 non-specific mechanical disruptors selected from the group consisting of Diatomaceous earth and kaolin; where the weight ratio of the overall amount of component A, calculated as dry matter, to the overall amount of pesticide B is preferably of from 100:1 to 1 :100, more preferably from 50:1 to 1 :10, even more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2.

15. The use as claimed in any of the preceding claims, where the invertebrate pests are selected from the group consisting of arthropods, gastropods and nematodes.

16. The use as claimed in claim 15, where the invertebrate pests are selected from the group consisting of harmful insects, arachnids, slugs, snails and nematodes; where the insects are preferably selected from the group consisting of herbivorous sucking insects, herbivorous piercing insects, herbivorous licking insects, herbivorous chewing insects, herbivorous rasping insects, wood-eating insects and mixed forms thereof, and where the arachnids are preferably selected from herbivorous mites.

17. The use of a mixture comprising magnesium phosphonate and calcium phospho- nate as defined in any of claims 1 to 13 as a synergist for a pesticide B as defined in claim 14.

18. A method for combating invertebrate pests, which method comprises treating the invertebrate pests, their habitat, plants, plant propagation material or environment or material which is to be protected or rid from infestation by said pests with a pesticidally effective amount of a mixture as defined in any of claims 1 to 14.

19. A mixture, comprising

A. as component A the mixture comprising magnesium phosphonate and calcium phosphonate as defined in any of claims 1 to 13; and

B. as component B at least one further pesticide B, where the pesticide B is selected from the group consisting of:

B.1 acetylcholine esterase inhibitors selected from the class of carbamates which are in turn selected from the group consisting of alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, iso- procarb, methiocarb, methomyl, metolcarb, oxamyl, primicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or selected from the class of organophosphates which are in turn selected from the group consisting of acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyr- ifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthi- on, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- 51

(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecar- bam, methamidaphos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxymethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimi- phos-methyl, profenofos , propetamphos, prothiofos, pyraclofos, pyri- daphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetra- chlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion;

B.2 GABA-gated chloride channel blockers selected from the class of cyclodiene organochlorines which are in turn selected from the group consisting of chlordane and endosulfan; or selected from the class of phenylpyra- zoles which are in turn selected from the group consisting of acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole and vaniliprole;

B.3 sodium channel modulators selected from the class of pyrethroids or pyre- thrins which are in turn selected from the group consisting of acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, beta-cyfluthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, th eta-cy permethrin, zeta-cypermethrin, cyphenothrin [(1 R)-trans- isomers], deltamethrin, em- penthrin [(EZ)- (1 R)- isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, kadathrin, metofluthrin, permethrin, phenothrin [(1 R)-trans- isomer], prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetrame- thrin [(1 R)- isomer], tralomethrin and transfl uthrin; or selected from the group consistng of DDT and methoxychlor;

B.4 nicotinic acetylcholine receptor (nAChR) competitive modulators selected from the class of neonicotinoids which are in turn selected from the group consisting of acetamiprid, clothianidin, dinotefuran, imidacloprid, niten- pyram, thiacloprid and thiamethoxam; or selected from the group consisting of nicotine, sulfoxaflor, flupyradifurone and triflumezopyrim;

B.5 nicotinic acetylcholine receptor (nAChR) allosteric modulators - Site I selected from the class of spinosyns which are in turn selected from the group consisting of spinetoram and spinosad;

B.6 glutamate-gated chloride channel (GluCI) allosteric modulators selected from the group consisting of abamectin, emamectin benzoate, lepimectin and milbemectin;

B.7 juvenile hormone mimics selected from the group consisting of hydroprene, kinoprene, methoprene, fenoxycarb and pyriproxyfen; 52

B.8 miscellaneous non-specific (multi-site) inhibitors selected from the group consisting of methyl bromide and other alkyl halides, chloropicrin, cryolite, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium borate, sodium metaborate, tartar emetic, dazomet and metam;

B.9 chordotonal organ TRPV channel modulators selected from the group consisting of pymetrozine and pyrifluquinazon;

B.10 mite growth inhibitors selected from the group consisting of clofentezine, di- flovidazin, hexythiazox and etoxazole;

B.11 microbial disruptors of insect midgut membranes selected from the group consisting of Bacillus thuringiensis and the insecticidal proteins they produce and Bacillus sphaericus;

B.12 inhibitors of mitochondrial ATP synthase selected from the group consisting of diafenthiuron, organotin miticides selected from the group consisting of azocyclotin, cyhexatin and fenbutatin oxide; propargite and tetradifon;

B.13 uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from the group consisting of chlorfenapyr, DNOC and sulflu- ramid;

B.14 nicotinic acetylcholine receptor (nAChR) channel blockers selected from the group consisting of bensultap, cartap hydrochloride, thiocyclam and thi- osultap-sodium;

B.15 inhibitors of chitin biosynthesis, type 0 selected from the group consisting of bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hex- aflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and tri- flumuron;

B.16 the inhibitors of chitin biosynthesis, type 1 buprofezin;

B.17 the moulting disruptor cyromazine;

B.18 ecdysone receptor agonists selected from the group consisting of chromaf- enozide, halofenozide, methoxyfenozide and tebufenozide;

B.19 the octopamine receptor agonist amitraz;

B.20 mitochondrial complex III electron transport inhibitors selected from the group consisting of hydramethylnon, acequinocyl, fluacrypyrim and bifena- zate;

B.21 mitochondrial complex I electron transport inhibitors selected from the group consisting of fenazaquin, fen pyroxi mate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad and rotenone;

B.22 voltage-dependent sodium channel blockers selected from the group consisting of indoxacarb and metaflumizone;

B.23 inhibitors of acetyl CoA carboxylase selected from the group consisting of spirodiclofen, spiromesifen, spiropidion and spirotetramat; 53

B.24 mitochondrial complex IV electron transport inhibitors selected from the group consisting of aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, calcium cyanide, potassium cyanide and sodium cyanide;

B.25 mitochondrial complex II electron transport inhibitors selected from the group consisting of cyenopyrafen and pyflubumide;

B.26 ryanodine receptor modulators selected from the group consisting of chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole;

B.27 the chordotonal organ modulator of undefined target site flonicamide;

B.28 the GABA-gated chloride channel allosteric modulator fluxametamide;

B.29 compounds of unknown or uncertain mode of action selected from the group consisting of azadirachtin, benzoximate, bromopropylate, chinome- thionat, dicofol and pyridalyl;

B.30 Baculoviruses selected from the group consisting of Cydia pomonella GV, Thaumatotibia leucotreta GV, Anticarsia gemmatalis MNPV and Helicover- pa armigera NPV;

B.31 the nicotinic acetylcholine receptor (nAChR) allosteric modulator - site II GS-omega/kappa HXTX-Hv1a peptide;

B.32 bacterial agents (non-Bt) of unknown or uncertain mode of action selected from the group consisting of Burkholderia spp and Wolbachie pipientis (Zap);

B.33 botanical essence including synthetic, extracts and unrefined oils with unknown or uncertain mode of action selected from the group consisting of Chenopodium ambrosioides near ambrosioides extract, fatty acid monoesters with glycerol or propanediol and Neem oil;

B.34 fungal agents of unknown or uncertain mode of action selected from the group consisting of Beauveria bassiana strains, Metarhizium anisopliae strain F52 and Paecilomyces fumosoroseus Apopka strain 97; and

B.35 non-specific mechanical disruptors selected from the group consisting of Diatomaceous earth and kaolin. where preferably the weight ratio of the overall amount of component A, calculated as dry matter, to the overall amount of pesticide B is of from 100: 1 to 1 : 100, preferably from 50:1 to 1 :10, more preferably from 30:1 to 1 :5, in particular from 20:1 to 1 :5 and specifically from 10:1 to 1 :2. Agricultural composition, comprising the mixture as claimed in claim 19 and at least one inert liquid and/or solid agriculturally acceptable carrier.