WO2016087270A1

WO2016087270A1 - Solid agrochemical composition for extended release of carbon dioxide

Info

Publication number: WO2016087270A1
Application number: PCT/EP2015/077529
Authority: WO
Inventors: Christian Sowa; Holger Kreusch; Ronald Wilhelm; Fabian Niedermair; Thomas Lichtenegger
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2014-12-04
Filing date: 2015-11-24
Publication date: 2016-06-09
Anticipated expiration: 2017-06-04
Also published as: AR102893A1

Abstract

The present invention relates to a solid agrochemical composition comprising a binder and a carbon dioxide source, containing a solid acid and a CO₃ ^2--salt; or a salt of a cationic acid with a CO₃ ^2--anion, and an insecticide; to a method for preparing said agrochemical composition; a method for controlling undesired insect or mite attack and/or for regulating the growth of plants, comprising the application of said agrochemical composition.

Description

Solid agrochemical composition for extended release of carbon dioxide Description

The present invention relates to a solid agrochemical composition comprising a binder and a carbon dioxide source, containing a solid acid and a C03^2_-salt; or a salt of a cationic acid with a CC"3^2"-anion, and an insecticide. Furthermore, the invention relates to a method for preparing said agrochemical composition by contacting the binder, the carbon dioxide source, the insecticide and optionally an organic carbon dioxide source. Further subject matter is a method for controlling undesired insect or mite attack and/or for regulating the growth of plants, wherein said agrochemical composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment. The present invention comprises combinations of preferred features with other preferred features. Bernklau et al. disclose in a publication (Disruption of Host Location of Western Corn Rootworm Larvae (Coleoptera: Chrysomelidae) with Carbon Dioxide, Ecology and Behaviour, 2004, 97(2):330-339) the application of effervescent powders, yeast and also organic carbon dioxide sources to attract pests occurring in the soil. Drawbacks of this prior art is a low storage and temperature stability of the compositions, a short carbon dioxide release period, as well a lack of adaptability to the circumstances of its application, e.g. the soil, the temperature and the humidity.

The object of the present invention was therefore to find a means of delivering carbon dioxide in a controlled and elongated manner by agrochemical compositions, whose characteristics should include high storage and temperature stability, as well as a high degree of adaptability to a given environment of application. Finally, these agrochemical compositions were aimed to be biodegradable to allow for repeated applications. This object was achieved by a solid agrochemical composition comprising

a) a binder;

b) a carbon dioxide source containing a solid acid and a CO3

or a salt of a cationic acid with a C03^2_-anion; and

c) an insecticide.

An agrochemical composition comprises a pesticidally effective amount of active ingredients, such as insecticides. The term "effective amount" denotes an amount of the composition or of the active ingredients, which is sufficient for controlling harmful insects on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the insect species to be controlled, the treated cultivated plant or material, the climatic condi- tions and the specific active ingredient used. The term active ingredient herein denotes biologically active substances that are usually toxic to a given target organism.

The agrochemical composition is solid. The expert clearly differentiates between a solid and a non-solid agrochemical composition, such as a liquid, a gel, a paste or putty. Usually, solid state of matter is characterized by a distinct structural rigidity and virtual resistance to deformation (that is changes of shape and/or volume). Usually, solids have high values both of Young's modulus (e.g. at least 0.1 GPa) and of the shear modulus of elasticity (e.g. at least 0.01 GPa).

The binder may be a thermoplastic and may be selected from biopolymers or synthetic poly- mers. It may be solid at room temperature and may further exhibit a suitable melting temperature.

Thermoplastics are usually polymers that are pliable and moldable above a specific temperature and return to a solid state upon cooling. The polymer chains in thermoplastics are usually not covalently interconnected and the attracting forces between them are therefore often confined to non-covalent interactions.

The melting temperature of the binder may be from 40 to 150 °C, preferably from 50 to 120 °C, and most preferably from 60 to 100 °C.

As in this context, the term melting temperature refers to polymers with a stochastic contribution of oligomers and also to biopolymers with a mixture of different chemical substances, and therefore melting may occur over a vast temperature range. Hence, it is here emphasized that the term melting temperature designates the glass transition temperature of the substance, which is a parameter known to the skilled person.

The melting temperature may be measured by methods of common knowledge, such as differential scanning calorimetry (DSC) or differential thermal analysis (DTA), which have been described, for example, in ASTM E1356-08(2014) and DIN51007:1994-06. The kinematic viscosity of the binder within the temperature range from 50 to 120 °C may be from 10² to 10¹⁵ mPa-s, preferably from 10³ to 10¹² mPa-s and most preferably from 10³ to 10¹⁰ mPa-s. The binder may be selected from different chemical classes, such as waxes, polyketones, poly- amides, polyesters, polysaccharides, polyethers, polyamines, terpenes, as well as their chemical derivatives, their physical mixtures and compounds composed of at least two of these class members. The term waxes usually refers, but is not limited to, petroleum derived waxes, such as paraffin waxes, montan wax or polyethylene waxes, to silicon waxes, as well as to plant and animal waxes, such as lipids, fatty acids, fatty alcohols, esters of carboxylic acids with fatty alcohols and steroids and mixtures of these compounds.

Paraffin waxes are usually hydrocarbons, which may be linear or branched, saturated or aro- matic. Preferably, paraffin waxes are linear and saturated, and usually comply with the general formula CnHbn+n, wherein n is from 15 to 45 and are solid at 25 °C. By contrast, the index n is usually from 50 to 100 in polyethylene waxes.

Montan waxes are usually mixtures of non-glyceride long-chain carboxylic acid esters, free long-chain organic acids, long-chain alcohols, ketones and hydrocarbons and resins, such as resin acid. Herein, the term long-chain may refer to a range from C24 to C30.

Silicone waxes are typically alkylpolysiloxanes or arylpolysiloxanes or alkylarylpolysiloxanes. Herein, alkyl usually refers to a linear or branched alkyl moiety containing from 1 to 8 carbon atoms, preferably from 1 to 6. Furthermore, the term aryl refers to aromatic and cyclic moieties and their derivatives, containing from 5 to 10 carbon atoms in the cyclic aromatic. The siloxane scaffold may be branched or linear, preferably branched, and contain from 100 to 10,000 silicon atoms per molecule, preferably from 100 to 1000.

Examples of plant and animal waxes are bee wax, lanolin, spermaceti, sugar cane wax, jojoba wax, carnauba wax, candelilla wax, Japan wax, soy wax, and saturated and unsaturated fatty alcohols or acids, esters of fatty alcohols with fatty acids and esters of fatty acids with steroids.

Herein, the term "fatty" usually refers to chain lengths of the respective compound from 8 to 40 carbon atoms, preferably from 12 to 30, and most preferably from 14 to 25 carbon atoms.

Examples of saturated and unsaturated fatty alcohols or acids, esters of fatty alcohols with fatty acids and esters of fatty acids with steroids are myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, lignoceric acid, melissic acid, icosanoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolaidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, as well as the cholesterol, di- hydrocholesterol, lanosterol, dihydrolanosterol, agnosterol, dihydroagnosterol esters of the aforementioned fatty acids, and myricyl palmitate, cetyl palmitate, myricyl cerotate Preferred waxes are plant waxes, animal waxes and petroleum derived waxes, more preferably plant waxes and animal waxes and most preferably plant waxes.

Preferred plant and animal waxes are soy wax, carnauba wax and jojoba wax, more preferably carnauba wax. Polyesters are well-known polymers. They may comprise monomers in polymerized form, such as diols and diacids (or diesters), or hydroxyacids (or hydroxyesters). Preferably, the polyester is an aliphatic or a semiaromatic polyester.

Aliphatic polyesters typically include homopolymers of aliphatic hydroxycarboxylic acids or lac- tones, and also copolymers or block copolymers of different hydroxycarboxylic acids or lactones or mixtures of these. These aliphatic polyesters may also contain units of diols and/or of isocya- nates. The aliphatic polyesters may also contain units which derive from tri- or polyfunctional compounds, for example from epoxides, from acids or from triols. The aliphatic polyesters may contain the latter units as individual units, or a number of these, possibly together with the diols and/or isocyanates. Processes for preparing aliphatic polyesters are known to the skilled worker. In preparing the aliphatic polyesters it is, of course, also possible to use mixtures made from two or more co-monomers and/or from other units, for example from epoxides or from polyfunctional aliphatic or aromatic acids, or from polyfunctional alcohols. Examples of aliphatic polyesters are polymeric reaction products of lactic acid, 3- hydroxybutyrate, 4-hydroxybutyrate, caprolactone, or polyesters built up from aliphatic or cyclo- aliphatic dicarboxylic acids and from aliphatic or cycloaliphatic diols, such as polybutylene succinate. The aliphatic polyesters may also be random or block copolyesters which contain other monomers. The proportion of the other monomers is generally up to 10 percent by weight. Pre- ferred monomers are hydroxycarboxylic acids or lactones or mixtures of these.

Polymeric reaction products of lactic acid, 3-hydroxybutyrate, 4-hydroxybutyrate and caprolactone, are known per se or may be prepared by processes known per se. Besides homopolymers of the aforementioned monomers, also copolymers or block copolymers with other mono- mers are possible. By way of example, the polyester may comprise 3-hydroxyvaleric acid, in particular with a proportion by weight of up to 30 percent, preferably up to 20 percent. Suitable polymers of this type also include those with R-stereospecific configuration. Polyhy- droxybutyrates or copolymers of these can be prepared microbially. Processes for the preparation from various bacteria and fungi are known as well as a process for preparing stereospecific polymers. It is also possible to use block copolymers of the above-mentioned hydroxycarboxylic acids or lactones, or of their mixtures, oligomers or polymers.

Suitable co-polyesters built up from aliphatic or cycloaliphatic dicarboxylic acids and from aliphatic or cycloaliphatic diols are those built up from aliphatic or cycloaliphatic dicarboxylic acids or from mixtures of these, and from aliphatic or cycloaliphatic diols, or from mixtures of these. According to the invention either random or block copolymers may be used. Suitable aliphatic dicarboxylic acids according to the invention generally have from 2 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. They may be either linear or branched. For the purposes of the present invention, cycloaliphatic dicarboxylic acids which may be used are generally those having from 7 to 10 carbon atoms, and in particular those having 8 carbon atoms. However, in principle use may also be made of dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms. Examples which should be mentioned are: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1 ,3-cyclopentanedicarboxylic acid, 1 ,4- cyclohexanedicarboxylic acid, 1 ,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornanedicarboxylic acid, preferably adipic acid.

Mention should also be made of ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids, which may likewise be used, in particular the di-C1-C6-alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-tert-butyl, di-n- pentyl, diisopentyl and di-n-hexyl esters. Anhydrides of the dicarboxylic acids may likewise be used. The dicarboxylic acids or ester forming derivatives of these may be used individually or as a mixture of two or more of these.

Suitable aliphatic or cycloaliphatic diols generally have from 2 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. They may be either linear or branched. Examples are 1 ,4-butanediol, ethylene glycol, 1 ,2- or 1 ,3-propanediol, 1 ,6-hexanediol, 1 ,2- or 1 ,4-cyclohexanediol or mixtures of these.

Examples of aliphatic polyesters which may be used are aliphatic co-polyesters as described in WO 94/14870, in particular aliphatic co-polyesters made from succinic acid, from its diesters, or from mixtures with other aliphatic acids or, respectively, diesters, for example glutaric acid and butanediol, or mixtures made from this diol with ethylene glycol, propanediol or hexanediol or mixtures of these. The term semiaromatic polyesters may refer to polyester, which comprises aliphatic and aromatic monomers in polymerized form, such as polybutylenadipatterephthalate. The term semiaromatic polyesters is also intended to include derivatives of semiaromatic polyesters, such as semiaromatic polyetheresters, semiaromatic polyesteramides, or semiaromatic polyetherester- amides. Among the suitable semiaromatic polyesters are linear non-chain-extended polyesters (WO 92/09654). Preference is given to chain-extended and/or branched semiaromatic polyesters. The latter are disclosed in the specifications mentioned in, for example, WO 96/15173, WO 96/15174, WO 96/15175, WO 96/15176, WO 96/21689, WO 96/21690, WO 96/21691 , WO 96/21689, WO 96/25446, WO 96/25448, and WO 98/12242, expressly incorporated herein by way of reference. Mixtures of different semiaromatic polyesters may also be used. In particular the term semiaromatic polyesters is intended to mean products such as Ecoflex® (BASF SE) and Eastar® Bio and Origo-Bi (Novamont). Further semiaromatic polyesters expressly incorporated herein are defined in WO 201 1/070091 .

The preparation of semiaromatic polyesters is of common knowledge and has been described, for example, in W096/15173.

Preferred polyesters are polylactic acid, polycaprolactone, polybutylene succinate and poly- butylenadipat-terephthalate, more preferably polylactic acid, polycaprolactone and polybutylenadipatterephthalate and especially preferably polycaprolactone and polybutylenadipatterephthalate. A particularly preferred polyester is polycaprolcatone.

The term polycaprolactone may refer either to homopolymers of caprolactone in polymerized form or to a polymer comprising caprolactone and a polyol, such as glycerol, butane-1 ,4-diol, neopentyl glycol or 1 1 1-trimethylolpropane, in polymerized form.

Preferably, the polycaprolactone is either a homopolymer of caprolactone in polymerized form or a polymer comprising caprolactone and neopentyl glycol in polymerized form. More preferably, the polycaprolactone is a homopolymer of caprolactone.

Usually, the polyester has a mass average molar mass of 2,000 to 100,000 g/mol, preferably from 2,000 to 60,000 and more preferably from 2,000 to 50,000 g/mol.

Usually the binder is selected from waxes and polyesters, preferably from animal and plant waxes and polyesters, more preferably from animal and plant waxes and polyester selected from polylactic acid, polycaprolactone, polybutylene succinate and polybutylenadipatterephthalate. In an especially preferred embodiment, the binder is selected from plant and animal waxes and polyesters selected from polycaprolactone and polybutylenadipatterephthalate, and in particular the binder is selected from plant waxes and polycaprolactone. By way of example, the binder may be selected from soy wax, carnauba wax, jojoba wax and a polyester selected from polylactic acid, polycaprolactone, polybutylene succinate and polybutylenadipatterephthalate; preferably the binder may be selected from carnauba wax and a polyester selected from polycaprolactone and polybutylenadipatterephthalate, more preferably from carnauba wax and polycaprolactone.

The term binder used herein may also refer to a mixture of two or more different binders.

The concentration of the binder (a) in the agrochemical composition may be in the range from 20 to 99 wt% with regard to the total mass of the agrochemical composition, preferably from 30 to 99 wt% and especially preferably from 40 to 95 wt% of the agrochemical composition.

The carbon dioxide source is a mixture of a solid acid and a C03^2_-salt; or a salt of a cationic acid with a C03^2_-anion.

The term solid acid usually refers to acids that are solid at room temperature and whose melting temperature may be in the range from 40 to 150 °C, preferably from 50 to 120 °C, and most preferably from 60 to 100 °C.

Usually, the solid acid is a solid organic acid. Examples of solid organic acids are tartaric acid, citric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, succinic acid, lactic acid, malic acid, oketoglutaric acid, oxaloacetic acid, phthalic acid, terephthalic acid, fumaric acid, aspartic acid, glutamic acid, benzoic acid, nicotinic acid, abietic acid and salicylic acid. Preferred solid organic acids are tartaric acid, citric acid, malic acid, and oxalic acid, more preferably tartaric acid and citric acid and especially preferably tartaric acid. Usually, the Lewis acidity of the solid acid refers to a value below 14, preferably below 10 and most preferably below 6.

Examples of C0₃ ² -salts are LiCOs, LiHCOs, Na₂C0₃, NaHCOs, K₂C0₃, KHCOs MgCOs, CaCOs, SrCOs, MnCOs and FeCOs.

Preferred C0₃ ²--salts are Na₂C0₃, NaHCOs, K₂C0₃, KHCOs, and CaCOs, more preferred

Na₂COs, NaHCOs, K₂COs, KHCOs, and CaCOs, especially preferred Na₂COs, K₂COs and CaCOs and in particular CaCOs. The term cationic acid usually refers to positively charged ions displaying Lewis acidity, such as NH4⁺-, methylammonium- or pyridinium-ions. Preferably, the term Lewis acidity of the cationic acid refers to a pK_s value below 14, more preferably below 12 and most preferably below 10.

In one form of the invention, the carbon dioxide source is a mixture of a solid organic acid and a C03²"-salt. In another form of the invention, the carbon dioxide source is a salt of a cationic acid with a C03^2"-ion, such as NH4CO3 and NH4(HC03). In a preferred form of the invention, the carbon dioxide source is a mixture of a solid organic acid selected from tartaric acid, citric acid, malic acid and oxalic acid with a C03^2"-salt selected from Na2C03, NaHC03, K2CO3, KHCO3, and CaCOs; or of a salt of a cationic acid with a C03^2"-ion, such as NH4CO3 and NH4(HC03). In a more preferred form of the invention, the carbon dioxide source is a mixture of a solid or- ganic acid selected from tartaric acid and citric acid with a CC"3^2"-salt selected from Na2C03, K2CO3, and CaCOs; or NH4CO3.

In one embodiment, the carbon dioxide source does not comprise NH4CO3.

By one way of example, the carbon dioxide source is a mixture of a solid organic acid selected from tartaric acid or citric acid, and a C03^2_-salt; more preferably a mixture of a solid organic acid selected from tartaric acid or citric acid, and a C03^2"-salt selected from Na2C03, NaHC03, K2CO3, KHCO3, and CaCOs; most preferably a mixture of a solid organic acid selected from tartaric acid and citric acid with CaCC"3.

In an especially preferred form of the invention, the carbon dioxide source is a mixture of tartaric

The concentration of the carbon dioxide source (b) in the agrochemical composition may be in the range from 1 to 80 wt% with regard to the total mass of the agrochemical composition, preferably from 5 to 70 wt% and especially preferably from 5 to 50 wt% of the agrochemical composition.

The molar ratio of the solid acid and CO3²- may be from 10 1 to 1/10, preferably from 5/1 to 1/2 and most preferably from 3/1 to 1/1.

Suitable insecticides for the present application are known to the skilled person and can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. They may be selected from the class of carbamates, organophosphates, organo- chlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, mil- bemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymet- rozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives.

Mixtures of insecticides of two or more of the abovementioned classes, as well as two or more members of one class may also be used.

In one embodiment, the insecticide is selected from neonicotinoides, such as acetamiprid, thia- methoxam, clothianidin, imidacloprid, thiacloprid, dinotefuran, and netenpyram. In another em- bodiment, the insecticide is selected from fiproles, such as fipronil, ethiprole, flufiprole, pyra- fluprole, and pyriprole. In yet another embodiment, the insecticide is selected from compounds with unknown or uncertain mode of action, such as afidopyropen, afoxolaner, azadirachtin, ami- doflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, di- cloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradi- furone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, and triflumezopyrim, preferably broflanilide. In yet another embodiment, the insecticide is selected from pyrethroids, such as cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, permethrin, phenothrin, and pyrethrin (pyrethrum). In one embodiment, the insecticide is not boric acid, metaboric acid, their salts, or boron triox- ide. In another embodiment, the insecticide is an organic compound.

The insecticide is typically solid and may have a melting temperature of at least 30 °C, preferably of at least 50 °C and more preferably of at least 60 °C.

The concentration of the insecticide (c) in the agrochemical composition may be in the range from 0,001 to 90 wt% with regard to the total mass of the agrochemical composition, preferably from 0,01 to 10 wt% and especially preferably from 0,1 to 5 wt% of the agrochemical composition.

In one embodiment of the present invention, the agrochemical composition contains

a) the binder selected from animal or plant waxes and polyesters;

b) the carbon dioxide source containing a solid acid and a C03²"-salt;

or a salt of a cationic acid with a C03^2_-anion; and

c) the insecticide.

In yet another embodiment of the present invention, the agrochemical composition contains a) the binder; the carbon dioxide source containing a solid acid selected from citric or tartaric acid and

the insecticide.

In yet another embodiment of the present invention, the agrochemical composition contains a the binder selected from animal or plant waxes and polyesters;

b the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0₃ ²--salt; and

c the insecticide.

In yet another embodiment of the present invention, the agrochemical composition contains a the binder selected from carnauba wax and polycaprolactone;

b the carbon dioxide source containing a solid acid and a C03²"-salt,

or a salt of a cationic acid with a C03^2_-anion; and

c the insecticide.

b the carbon dioxide source containing a solid acid selected from citric or tartaric acid and

c the insecticide.

b the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0₃ ²--salt selected from Na₂C0₃, NaHCOs, K₂C0₃, KHCOs, and CaC0₃; and c the insecticide.

In yet another embodiment of the present invention, the agrochemical composition contains the binder selected from carnauba wax and polycaprolactone;

tartaric acid and CaCOs; and

the insecticide.

The agrochemical composition may further contain an organic carbon dioxide source (d), which may be selected from mono-, oligo- and polysaccharides. Chemical derivatives (e.g. obtainable by alkylation, oxidation, etherfication, esterification, sulfatation, nitration, amination and ami- dation) of the aforementioned substances are also within the scope of the invention.

Examples of mono-, oligo- and polysaccharides are glucose, fructose, arabinose, mannose, galactose, cellobiose, saccharose, maltose, lactose, trehalose, amylose, amylopectin, starch, glycogen, pectin, chitin, callose, agarose, sinistrin, cellulose, dextrane or xanthane, potato flour and cereal flours. Starch comprises preferably one or more of corn, potato, wheat, rice, sago, tapioca, waxy maize, sorghum, and cassava starch.

Typical examples of cereal flours are flours produced from maize, rice, wheat, barley, sorghum, millet, oats, rye, triticale, buckwheat, fonio, quinoa, amaranth, einkorn, spelt, durum and emmer.

Preferred organic carbon dioxide sources are saccharose, maltose, lactose, starch, cellulose, potato flour and cereal flours. More preferred organic carbon dioxide sources are saccharose, lactose, cellulose, potato flour and cereal flours. Most preferred as organic carbon dioxide sources are saccharose, cellulose and cereal flour, especially preferred saccharose and cereal flour, and in particular saccharose and wheat flour.

Usually the agrochemical composition comprises from 1 to 70% by weight of the organic carbon dioxide source, preferably from 5 to 50% and especially preferably from 5 to 30% of the carbon dioxide source, in each case based on the total weight of the agrochemical composition.

The components (a), (b), (c), and optionally (d) are usually homogeneously distributed in the agrochemical composition. The term "homogeneous" relates to a thorough mixture of the components, e.g. obtainable by extrusion. Thus, the term homogeneous typically does not only relate to a even distribution on a molecular level, but also to heterogenic mixtures with a statistically even spatial distribution.

a) the binder selected from animal or plant waxes and polyesters;

b) the carbon dioxide source containing a solid acid and a C03^2"-salt,

or a salt of a cationic acid with a C03^2_-anion;

c) the insecticide; and

d) the organic carbon dioxide source, selected from saccharose, maltose, lactose, starch, cellulose, potato flour and cereal flour.

In another embodiment of the present invention, the agrochemical composition contains

a) the binder selected from carnauba wax or polycaprolactone;

b) the carbon dioxide source containing a solid acid and a C03^2"-salt,

or a salt of a cationic acid with a C03^2_-anion;

c) the insecticide; and

d) the organic carbon dioxide source, selected from saccharose, maltose, lactose, starch, cellulose, potato flour and cereal flour. In yet another embodiment of the present invention, the agrochemical composition contains a) the binder selected from carnauba wax or polycaprolactone;

b) the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0₃ ²--salt selected from Na₂C0₃, NaHCOs, K₂C0₃, KHCOs, and CaC0₃;

c) the insecticide; and

d) the organic carbon dioxide source, selected from saccharose, lactose, cellulose, potato flour and cereal flours.

In yet another embodiment of the present invention, the agrochemical composition contains a) the binder;

b) the carbon dioxide source containing a solid acid and a C03²"-salt,

or a salt of a cationic acid with a C03^2_-anion;

c) the insecticide; and

d) the organic carbon dioxide source, selected from saccharose, cellulose and cereal flours.

In yet another embodiment of the present invention, the agrochemical composition contains a) the binder selected from carnauba wax or polycaprolactone;

c) the insecticide; and

b) tartaric acid and CaCOs;

c) the insecticide; and

d) the organic carbon dioxide source, selected from saccharose and wheat flour.

The concentration of the components (a), (b), (c) and (d) in the agrochemical composition may comprise from 20 to 99 wt% of the binder (a), from 5 to 70 wt% of the carbon dioxide source (b), from 0,001 to 90 wt% of the insecticide (c), and optionally from 1 to 70 wt% of the organic carbon dioxide source (d).

Preferably, the agrochemical composition comprises from 40 to 95 wt% of the binder (a), from 5 to 70 wt% of the carbon dioxide source (b), from 0,01 to 10 wt% of the insecticide (c), and optionally from 1 to 70 wt% of the organic carbon dioxide source (d). More preferably, the agrochemical composition comprises from 40 to 95 wt% of the binder (a), from 5 to 50 wt% of the carbon dioxide source (b), from 0,1 to 5 wt% of the insecticide (c), and optionally from 1 to 70 wt% of the organic carbon dioxide source (d).

Especially preferably, the agrochemical composition according to the invention comprises from 40 to 95 wt% of the binder (a), from 5 to 50 wt% of the carbon dioxide source (b), from 0,1 to 5 wt% of the insecticide (c), and optionally from 5 to 50 wt% of the organic carbon dioxide source (d).

In one form of the invention, the agrochemical composition comprises from 5 to 70 wt% of the carbon dioxide source (b), and from 5 to 50 wt% of the organic carbon dioxide source (d).

In another form of the invention, the agrochemical composition comprises from 5 to 50 wt% of the carbon dioxide source (b), and from 5 to 50 wt% of the organic carbon dioxide source (d). In yet another form of the invention, the agrochemical composition comprises from 5 to 50 wt% of the carbon dioxide source (b), and from 5 to 30 wt% of the organic carbon dioxide source (d) The agrochemical composition may be biodegradable. For the purposes of the present invention, a substance or a mixture of substances complies with the feature termed "biodegradable", if this substance or the mixture of substances has a percentage degree of biodegradation of at least 90 wt% within 6 months under aerobic conditions according to the processes defined in DIN EN 13432:2000 and DIN EN ISO 14855:1999.

The result of the biodegradability is generally that the agrochemical composition breaks down within an appropriate and demonstrable period. The degradation may be brought about enzy- matically, hydrolytically, oxidatively, and/or via exposure to electromagnetic radiation, such as UV-radiation, and is most predominantly caused by exposure to microorganisms, such as bac- teria, yeasts, fungi, and algae. An example of a method of quantifying the biodegradability mixes a sample with soil and stores it for a particular time. By way of example, the release of CO2 as a measure of biodegradation of the sample can be analyzed according to Guideline OECD 301 :1992 (301 F Manometric Respiratory Test). Herein, a sample is mingled with soil and inserted into a bottle that is subsequently hermetically closed. The bottle further contains a CO2 ab- sorbing reservoir, such as sodium hydroxide, to remove evolved CO2 from the internal atmosphere. The head of the bottle further contains a valve for inserting oxygen in order to maintain the pressure and oxygen concentration in the bottle. The amount of consumed oxygen can be quantitatively measured over a given time period to calculate the degree of biodegradation of the sample. Alternatively, no further oxygen is supplied during the experiment and the partial vacuum in the bottle is measured in the bottle head. The agrochemical composition may further be prepared as a granulate containing components (a), (b), (c) and optionally (d). The granulate may be of any shape, preferably of tubular shape.

The granules may have a granule diameter up to 20 mm, more preferably up to 10 mm and es- pecially preferably up to 5 mm. The granule diameter may be at least 0.01 mm, preferably at least 0.1 mm and more preferably at least 1 mm. The term granule diameter refers either to the length or the width of the granulate, whatever dimension is longer.

When employed in plant protection, the amount of insecticides applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.05 to 0.5 kg per ha. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 to 2 kg, preferably 0.005 to 1 kg, of active substance per cubic meter of treated material.

The amount of granulate applied is usually from 1 to 500 kg per ha, more preferably from 1 to 200 kg per ha, and most preferably from 1 to 10 kg per ha.

Various types of further attractants, fertilizers, bittering agents, or solid carriers may be added to said agrochemical composition. These agents can be admixed with the agrochemical composition according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.

Suitable further attractants are non-pesticidal materials which may act in one or several of the following ways: a) entice the insect to approach the agrochemical composition or the material treated with the agrochemical composition; b) entice the insect to touch the agrochemical composition or the material treated with the agrochemical composition; c) entice the insect to consume the agrochemical composition or the material treated with the agrochemical composition; and d) entice the insect to return to the agrochemical composition or the material treated with the agrochemical composition. Suitable attractants include non-food attractants and food at- tractants, also termed as feeding stimulants.

Suitable non-food attractants are usually volatile material. The volatile attractants act as a lure and their type will depend on the pest to be controlled in a known manner. Non-food attractants include for example flavors of natural or synthetic origin. Suitable flavors include meat flavor, yeast flavor, seafood flavor, milk flavor, butter flavor, cheese flavor, onion flavor, and fruit flavors such as flavors of apple, apricot, banana, blackberry, cherry, currant, gooseberry, grape, grapefruit, raspberry and strawberry. Suitable food attractants are proteins, including animal proteins and plant proteins, e. g. in the form meat meal, fish meal, fish extracts, seafood, seafood extracts, or blood meal, insect parts, crickets powder, yeast extracts, egg yolk, protein hydrolysates, yeast autolysates, gluten hy- drolysates, and the like;

Bittering agents serve to avoid incidental consumption by humans. Especially preferred is dena- tonium benzoate, which, in a suitable concentration (in general 1 to 200 ppm, in particular 5 to 20 ppm), has a most unpleasant taste for humans.

Colorants are frequently added, and the agrochemical composition is thereby clearly logged as not for consumption, in order to avoid ingestion by mistake by humans or non-targeted animals. In particular, blue colorants serve to deter birds.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and mixtures thereof.

The present invention further relates to a method for preparing said agrochemical composition by contacting the binder (a), the carbon dioxide source (b), the insecticide (c) and optionally the organic carbon dioxide source (d).

The contacting may be achieved in a known manner, such as described by Mollet and Grube- mann, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection formulation, Agrow Reports DS243, T&F Informa, London, 2005. Usually, the contacting can be achieved by mixing, grinding or by use of an extruder.

The method for preparing the agrochemical composition may further comprise heating of the agrochemical composition to a temperature from 40 to 150 °C, preferably from 50 to 120 °C, and most preferably from 60 to 100 °C.

Mixing may be done by the use of a ribbon blender, a V-blender, a continuous processor, a cone screw blender, a screw blender, a double cone blender, a double planetary, a high viscosity mixer, a counter-rotating mixer, a double or a triple shaft mixer, a vacuum mixer, a high- shear-rotor-stator, a paddle mixer, a jet mixer, a drum blender, a banbury mixer, an interim mix- er or a planetary mixer.

Grinding may be done to the mixture in typical milling devices, such as ball mills, bead mills, rod mills, semi- and autogenous mills, pebble mills, grinding roll mills, Buhrstone mills, tower mills, hammer mills, planetary mills, vertical-shaft-impactor mills, colloid mills, cone mills, disk mills, edge mills, jet mills, pellet mills, stirred mills, three roll mills, vibratory mills, Wiley mills or similar milling and grinding devices known by the skilled person. The method for preparing the agrochemical composition may comprise extrusion, applied to a mixture, which contains the binder (a), the carbon dioxide source (b), the insecticide (c) and optionally the organic carbon dioxide source (d). Usually, the process further comprises cooling of the extruded or pelleted mixture.

Extrusion is usually performed by use of extruders, which are well known in the art. Examples of extruders are ram extruders, planetary-gear extruders, one screw and twin screw extruders. Typically, the extrusion is accomplished at a pressure (usually taken just before entering into the extrusion grid) from 1 to 80 bars, preferably from 1 to 60 bars, and more preferably from 1 to 40 bars. Typically, the extrusion is accomplished at a temperature from 40 to 150 °C, preferably from 50 to 120 °C, and more preferably from 60 to 100 °C. Said temperature refers to the paste during extrusion. When necessary, the temperature is maintained at the desired value by cooling. An extrusion grid may be used with holes of any shape, preferably of circular shape. The diameter of the holes is usually up to 20 mm, preferably up to 10 mm and more preferably up to 5 mm.

The continuous extrudate may be collected on a moving cylinder or on a conveyor belt. Typically, it is subsequently cut, e.g. with a rotating knife, into shorter sticks before or after cooling, preferably after cooling. In the case of circular holes, the spaghetti-shaped extrudate may be cut into cylindrical shape. In case of polygonal holes (e.g. triangular or rectangular), the extrudate may be cut into corresponding shapes. The resulting pellets might be broken into shorter granules before or after drying, preferably after drying.

The present invention further relates to a method of controlling undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment. Herein, the agrochemical composition is preferably allowed to act on the soil. More preferably, the agrochemical composition is mixed into the soil; most preferably the agrochemical composition is mixed into the soil before or concomitant to sowing. In particular the agrochemical composition is mixed into the soil concomitant to sowing. Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or goose- berries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tange- rines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweet leaf (Ste- via rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested produce of these plants. In one embodiment, the crop plant is a maize plant.

The term crop plants also includes those plants, which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products, which are on the market or in the process of being developed. Genetically modified plants are plants whose genetic material has been modified in a manner, which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material). Here, one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties. Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.

The insects or mites may be from the order of coleoptera, diptera, hemiptera, and homoptera, more preferably from the order coleoptera. In one embodiment, the agrochemical composition is used for combating corn root worm {Diabrotica virgifera).

Further subject matter is the use of said agrochemical composition for combating undesired insects or mites. The advantages of the agrochemical composition according to the invention are a high storage and temperature stability, a high adaptability towards the application, e.g. the soil, the temperature and the humidity. The agrochemical composition does not degas toxic substances; and it can be easily prepared by extrusion. Further advantages are an extended and constant carbon dioxide release over time (e.g. at least two months, preferably at least 3 months), the instant onset of CO2 production at the time of application, and the biodegradability of the agrochemical composition. The following examples are intended for illustration and do not limit the scope of the invention.

Examples:

PCL: Polycaprolactone, Mw approximately 40,500 g/mol, MW/MN=2.6.

Cellulose: Unmodified microcrystalline cellulose

Flour: Wheat flour type 405

Effervescent powder: Ground mixture of tartaric acid and calcium carbonate with a molar ratio of 2/1.

Dispersant 1 : Sodium salt of a water-soluble cross-linked phenol polymers containing sulfonic acid moieties

Dispersant 2: 25% aqueous solution of sodium salt of an anionic copolymer of maleic acid and an olefin; pH 10.5; viscosity 50 mPas

Preservative: Sodium docusate Example-1 : Preparation of CQ2-releasing granulate

Granulates G1 -G12 were prepared according to Table 1 . To this end, the effervescent powder was premixed with the polysaccharides (wheat flour, saccharose or cellulose) to a macroscopi- cally homogeneous mixture. Optionally, an insecticide in form of a granulate or a powder could be added to the premix. For extrusion of this premix with PCL, a Micro Compounder (Haake MiniLab) was heated to 70 °C at 25 rpm, and both the PCL and the premix were inserted alter- natingly by a funnel. Homogenization was achieved by circulation of the mixture at 100 rpm for 5 minutes. Subsequently, the speed was again decreased to 25 rpm and the tubular product was obtained by conducting it through a circular bypass and collecting it on a plastic roll. After cooling and solidification of the material, it was granulated to pieces of approximately 3-5 mm diameter.

Table 1 : Granule compositions (all concentrations in [wt%])

Granulate No PCL Wheat Flour Saccharose Cellulose Effervescent Powder

G1 60 20 - - 20

G2 75 12.5 - - 12.5

G3 75 12.5 - - 12.5

G4 60 - 20 - 20

G5 75 - 12.5 - 12.5

G6^* 90 - 10 - -

G7 75 - - 12.5 12.5

G8 75 - - 12.5 12.5 G9^* 90 - - 10 -

G10 75 - - - 25

G1 1 90 - - - 10

G12^* 100 - - - -

Comparative Example not according to the invention

Example-2: Preparation of CQ2-releasing granulate containing Broflanilide

Granulates G13-G15 were prepared according to Table 2. To this end, the effervescent powder was premixed with Broflanilid and the wheat flour to a macroscopically homogeneous mixture. For extrusion of this premix with PCL, a Micro Compounder (Haake MiniLab) was heated to 70 °C at 25 rpm, and both the PCL and the premix were inserted alternatingly by a funnel. Homog- enization was achieved by circulation of the mixture at 100 rpm for 5 minutes. Subsequently, the speed was again decreased to 25 rpm and the tubular product was obtained by conducting it through a circular bypass and collecting it on a plastic roll. After cooling and solidification of the material, it was granulated to pieces of approximately 3-5 mm diameter.

Table 2: Granule compositions (all concentrations in [wt%])

Example-3: Measurement of controlled CO2 release and biodegradability

The experiments were performed according to Guideline OECD 301 :1992. In a first step, the carbon contents of granulates G1 , G2, G4, G5 and G10 were determined by standard quantitative elemental analysis. Subsequently, a quantity of granulates equivalent to 45 mg of carbon content was thoroughly mixed with 56 g of soil (pH 6.8) and inserted into an Oxitop^® flask. Such flasks are composed of a 250 ml GL45 bottle and a bottle head containing a C02-absorber reservoir and a pressure measuring device. The C02-absorber reservoir was filled with one gram of sodium hydroxide, which absorbed any produced CO2 during the experiment, and the bottle heads were screwed onto the bottles. Samples were incubated at 20 °C for 15 days in triplicates. Table 3 displays the partial vacuum of the samples in percent compared to a sample con- taining only soil and no granule, which corresponds to a value of 100%. Table 3

Table 3 demonstrated that all granulates decayed by releasing CO2 during the specified time period, depending on their respective compositions, e.g. their organic carbon dioxide source and the concentration of effervescent powder. Hence, the CO2 release pattern can be adapted to the application and environmental conditions.

Example-4: Measurement of controlled CO2 release and biodegradability after different time periods

The experiments were performed with granules G3, G4, G8, as well as with the comparative granules G9^* and G12^*, as described in Example-3. In this experiment, however, the incubation periods were 10 days, 30 days and 50 days at 20 °C for each sample. Table 4 displays the additional partial vacuum of the samples in percent compared to a sample containing only soil and no granule, which corresponds to a value of 0%.

Table 4

^*Comparative Example not according to the invention

The results demonstrated that a constant release of CO2 was acchieved by the produced gran- ules. Compared to granules consisting of a binder only, more CO2 is released and the release starts earlier. The release was steady over a long time period.

Comparative Example-5:

Comparative granules G16^* were produced with the ingredients according to Table 5. The in- gredients were mixed and the mixture was submitted to extrusion according to Example 1. The granules did not contain a binder nor an effervescent powder. Table 5: Composition of granules G16^*

Example-6: Measurement of controlled CO2 release after different time periods

The experiments were performed with granules G13, G14, G15, as well as with the comparative granules G12^* and G16^*, as described in Example-4. Table 6 displays the additional partial vacuum of the samples in percent compared to a sample containing only soil and no granule, which corresponds to a value of 100%.

Table 6

The results demonstrated that a constant and linear release of CO2 was acchieved by the produced granules G13, G14, and G15. Compared to granules consisting of a binder only (G12^*), more CO2 is released and the release starts earlier. The production of CO2 from Granules G12^* demonstrates their biodegradability in the soil. Granules containing no binder nor effervescent powder (G16^*) displayed a non-linear release of CO2 that led to an early onset of saturation of the release curve.

Claims

1. A solid agrochemical composition comprising

a) a binder selected from animal or plant waxes, and polyesters;

b) a carbon dioxide source containing a solid acid and a C03^2"-salt,

or a salt of a cationic acid with a C03^2_-anion; and

c) an insecticide.

2. The agrochemical composition according to claim 1 comprising as further component d) an organic carbon dioxide source selected from mono-, oligo- and polysaccharides.

3. The agrochemical composition according to claim 2, wherein the component d) is selected from saccharose, cellulose and cereal flours.

4. The agrochemical composition according to any of claims 1 to 3, where the components a), b), c), and optionally d) are homogeneously distributed within the agrochemical composition.

5. The agrochemical composition according to any of claims 1 to 4, wherein the polyester has a mass average molar mass from 2,000 to 60,000 g/mol.

6. The agrochemical composition according to any of claims 1 to 5, wherein the binder is car- nauba wax or polycaprolactone.

7. The agrochemical composition according to any of claims 1 to 6, wherein the binder is a thermoplastic substance with a melting temperature from 50 to 120 °C.

8. The agrochemical composition according to any of claims 1 to 7, wherein the solid acid is citric and/or tartaric acid.

9. The agrochemical composition according to any of claims 2 to 8, containing from 5 to 50 wt% of the carbon dioxide source (b) and from 5 to 50 wt% of the organic carbon dioxide source (d).

10. The agrochemical composition according to any of claims 1 to 9, where the agrochemical composition is a granulated material with a granule diameter up to 10 mm.

1 1. The agrochemical composition according to any of claims 1 to 10, where the molar ratio of the solid acid to the C0₃ ²--salt is from 5/1 to 1/2. A method for preparing the agrochemical composition as defined in any of claims 1 to 1 1 comprising the step of contacting the binder (a), the carbon dioxide source (b), the insecticide (c) and optionally the organic carbon dioxide source (d).

The method according to claim 12, further comprising the step of heating the agrochemical composition to a temperature from 50 to 120 °C.

A method of controlling undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical composition as defined in any of claims 1 to 1 1 is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on the crop plants and/or on their environment.