EP1976797A2

EP1976797A2 - Phyllosilicate formulations for the controlled release of active substances

Info

Publication number: EP1976797A2
Application number: EP07702708A
Authority: EP
Inventors: Arno Nennemann; Johan Kijlstra; Daniel Rudhardt; Frank Sicking
Original assignee: Bayer Technology Services GmbH
Current assignee: Bayer Intellectual Property GmbH
Priority date: 2006-01-14
Filing date: 2007-01-12
Publication date: 2008-10-08
Also published as: DE102006001941A1; US20090170705A1; WO2007080117A2; JP2009523147A; WO2007080117A3

Abstract

The invention relates to powdery active substance formulations which contain agorochemical, cosmetic, relevant material protective, veterinary, medical or pharmaceutically active substances and organically modified layer compounds. The invention also relates to methods for the production thereof and to the use thereof for the controlled release of active substances.

Description

Layered silicate formulation for controlled release of active ingredient

The present invention relates to powdered formulations of active substances which contain agrochemical, cosmetic, material protection-relevant, veterinary-medicinal or pharmaceutical active substances and organically modified layered compounds, processes for their preparation and their use for the controlled release of the active compounds.

The controlled release of active substances poses a major challenge for many applications. Applications for controlled release formulations can be found in agriculture, cosmetics, medicine and materials. Depending on the application, different goals may be important, such as:

• Controlled release of active ingredients

• reduction of toxicity

• Reduced decomposition of the active substance

• Reduced volatility of the active ingredient

• Reduced washout in soils

• Reduced odor of the formulation

• Reduced weathering vulnerability

• Easier handling

Phyllosilicates (bentonites, clay minerals) are used as carriers of active substances or as fillers in multicomponent formulations. The use as carriers / adsorbents for active substances and other organic molecules is given by the high specific surface area and the possibility of organic surface modification. The modification of layered silicates and the adsorption of organic molecules on layered silicates in general have led to a large number of publications (eg Siantar, DP, Feinberg, B., & Fripiat, JJ, Interaction between organic and inorganic pollutants in the clay interlayer). Clay Minerals, 42 (1994) 187-96.).

In drug formulations, both unmodified phyllosilicates and modified phyllosilicates are used. They also serve as a supplement to other formulation ingredients. In combination with polymers, synergistic effects occur with respect to the release behavior, since a more or less porous polymer matrix can additionally reduce the release.

Unmodified phyllosilicates are used in pesticide formulations along with various additives and stabilizers. For example, US Pat. No. 4,304,587 describes the use of unmodified phyllosilicates with polymers (polypropylene glycol, polyvinyl alcohol), alcohols (glycol), lactones and other compounds which serve primarily for shaping (thickening).

The disadvantage of the unmodified phyllosilicates is their low adsorption behavior of hydrophobic active ingredients.

In order to increase the adsorption of the hydrophobic active ingredients, modified phyllosilicates are used. The modification can be carried out, for example, by ion exchange with inorganic or organic ions. Hermosin, MC and Cornejo, J., for example, describe the improved adsorption of the anionic herbicide 2,4-D on montmorillonite and vermiculite by modification with decylammonium ions (Adsorption of the anionic herbicide 2,4-D alkylammonium clays.) In Proceedings of the 7th Euroclay Conference, ed. M. Störr, K.-H. Henning, and P. Adolfi, Dresden, 1991, pp. 491-5.).

This is only an example, many studies have been published for the adsorption of hydrophobic herbicides on organically modified phyllosilicates.

El Nahhai et al. modified Wyoming montmorillonite with low molecular weight aromatic cations such as BTMA and PTMA below the cation exchange capacity of clay minerals. They found an increased adsorption of the hydrophobic herbicides alachlor and metolachlor compared to alkylammonium-modified clay minerals. The leaching and the volatility of the herbicides have been reduced (El-Nahhal, Y., Nir, S., Margulies, L., & Rubin, B., Reduction of photodegradation and volatilization of herbicides in organo-clay formulations.) Appl Clay Sci., 14 (1999) 105-19; El-Nahhal, Y., Nir, S., Polubesova, T., Margulies, L., & Ruby, B., Leaching, phytotoxicity and weed control of new formulations of metolachlor J. Agr. F. Chem., (1997)).

Similarly, pesitzides could be stabilized against photodegradation. Margulies et al. describe the photostabilization of the active compounds by energy transfer onto coadsorbed organic cations (Margulies, L., Rozen, H., & Cohen, E., Energy transfer at the surface of clays and protection of pestieides from photodegradation, Nature, 315 (1985) ) 658-9). A modification with polyhydroxyaluminum ions (Pillared clays) resulted in a reduction in the leaching of the herbicide metolachlor compared to the commercial formulation (Nennemann, A., Mishael, Y., Nir, S., Rubin, B., Polubesova, T., Bergaya, F., van Damme, H., & Lagay, G., Clay-based formulations of metolachlor with reduced leaching., Applied Clay Science, 18, no. 5-6, (2001) 265-75).

Increased adsorption of the pesticide metolachlor was also achieved by the use of thermally treated bentonites and coagulation of bentonites with di- and trivalent ions and inclusion in aggregates (Nennemann, A., Kulbach, S., & Lagaly, G., Entrapping Pesticides by coagulating smectites, Applied Clay Science, 18, No. 5-6, (2001) 285-98; Bojemueller, E., Nennemann, A., & Lagaly, G., Enhanced pesticide adsorption by thermally modified bentonites. Appl. Clay Sci. 18, (2001), 277ff).

Nir et al. Solubilized anionic pesticide in cationic micelles and adsorbed on layered silicates. In this way, the leaching behavior of anionic herbicides into the soil could be reduced (Nir, S., Rubin, B., Mishael, YG, Undabeytia, T., Rabinovitch, O., & Polubesova, T. Controlled-release formulations of anionic herbicides. [WO 2002052939]., 2002.).

The cited prior art is focused on reducing the release by rain and preventing leaching of the formulation. In order to influence the amount of active substance released as a function of time, no results are reported in the above publications. The wash-out behavior is determined by spraying vertically placed soil columns, equilibration over a constant period of time and subsequent detection of the penetration of the active ingredient into the soil via bioassays. In the case of photolytic degradation is similar procedure, the formulations are initially treated with UV light.

Correspondingly prepared formulations showed time-dependent measurements of the known hyperbolic release behavior with high initial release rate and decreasing release over time. Disadvantage of this release behavior is an initially increased phytotoxicity and too low efficacy in the progression of the release.

The synergistic effect in release behavior with a polymeric matrix is used in some applications. So-called clay polymer nanocomposites provide a way to exploit this synergistic effect. Polymer clay nanocomposites can be prepared, for example, via interlamellar polymerization, solution or via compounding. By way of example, the following approaches are mentioned: Tsipursky et al. prepared matrix formulations by incorporating layered silicates via solution or melt into the polymer matrix (Tsipursky, SJ, Beall, GW, & Vinokour, El Intercalates and exfoliates formed with N-alkenyl amides and / or acrylate-functional pyrrolidones and allylic monomers, oligomers and copolymer and composite materials containing same. [US 5,849,830].

No. 5,160,529 describes an interlamellar polymerization for the encapsulation of pesticides. Phyllosilicates were mixed with polyol and polyisocyanate and a reaction was carried out to the polyurethane. This formed a permeable polymer shell containing the pesticide

In US2004-0231231 A active ingredient is adsorbed on layered silicate, this complex mixed with dissolved polymer and made from a controlled-release formulation with a long-term barrier for drug release, eg. For an attract-kill application.

Disadvantages of the latter formulations based on the combination of modified layer silicates with polymers is the increased price due to an additional formulation step and also a dilution effect by the polymer matrix which reduces the formulated amount of active ingredient.

According to the current state of the art, it is thus known that modified phyllosilicates retard the release of active substances. A release profile from such layered silicate formulations is determined by adsorption and desorption phenomena on the layered silicate supports and by diffusion of the active substance from the interlayer space. Disadvantage of these systems, however, is that the release rate is not adjustable. At the beginning significantly more active ingredient per unit time is released, the release rate then decreases continuously (hyperbolic course). As a result, a uniform supply, for example. The plant over a given period of time with constant amounts of active ingredient is not given. Another disadvantage of this release behavior is an initially increased risk of phytotoxicity as well as a too low effectiveness in the progression of the release.

Based on the known state of the art, the object is therefore to provide active compound layer compound formulations which not only retard the release of active ingredients even more, but also have a specifically adjustable release profile with a continuous release of active ingredient.

This object is achieved by the powder formulations according to the invention and the process for their preparation according to the independent claims, wherein the dependent claims represent preferred embodiments of the invention. The invention therefore powder formulations for the controlled, sustained release of active ingredients containing

at least two organically modified, inorganic layer compounds, each containing at least one active ingredient and

- optional additives

characterized in that they are obtainable by a manufacturing method in which

if an organically modified layer compound is dispersed in a separate solution of one or more active substances in a solvent or a solvent mixture,

in which

either the respective solvents or solvent mixtures differ from one another or

the organically modified inorganic layered compounds in at least one modifier or with the same modifiers differ in their compositional ratio or

the unmodified inorganic layer compounds on which the at least two organically modified, inorganic layer compounds are based differ, and

the respective solvent or solvent mixture is then separated off,

- The resulting powder of organically modified layer compound and active ingredient is homogenized and

the respective resulting powders from the different solvent or solvent mixtures approaches are mixed together.

The use of different solvents and solvent mixtures with otherwise identical preparation steps or in at least one modifier or - with the same modifiers - of varying in their composition ratio of modifiers organically modified inorganic layer compounds under otherwise identical conditions or in the underlying unmodified inorganic Layer compounds differing at least two organically modified, inorganic layer compounds in ansons- same conditions causes a different release behavior. A mixture of such formulations of individual formulations prepared with different solvents shows a slowed, continuous release whose profile can be controlled in a surprisingly simple manner by the composition of the mixture.

Preferred subject matter of the invention are also powder formulations for the controlled, sustained release of active substances containing

optionally additives

characterized in that they are obtainable by a manufacturing method in which

each an organically modified layer compound is dispersed in a separate solution of at least one active ingredient in a solvent or a solvent mixture,

wherein the respective solvents or solvent mixtures differ from one another and

the respective solvent or solvent mixture is then separated off,

the resulting powder of organically modified layer compound and active ingredient is homogenized and

the respective resulting powders from the different solvent or solvent mixture mixtures are mixed with one another.

The use of different solvents and solvent mixtures with otherwise identical production steps surprisingly causes a different release behavior with otherwise organically modified inorganic layered compound and similar inorganic layer compounds underlying the organically modified layer compounds in the respective resulting layer compound formulation and a mixture of such formulations of individual formulations prepared with different solvents shows a slowed, continuous release whose profile is controllable by the composition of the mixture. The invention likewise relates to powder formulations for the controlled, delayed release of active substances

- optional additives

characterized in that they are obtainable by a manufacturing method in which

wherein the organically modified inorganic layer compounds each carry one or more modifiers and the layer compounds in at least one modifier or with the same modifiers differ in their composition ratio, and

the respective solvent or solvent mixture is then separated off,

The use of such a powder formulation also causes a different release behavior. The at least one different modifier of the respective organically modified inorganic layered compounds or, in the case of identical modifiers, the modifiers differing in the composition ratio in the respectively resulting layer compound formulation with otherwise identical production steps in the same solvents and solvent mixtures and with the same inorganic layer compounds on which the organically modified layered compounds are based allows in the surprisingly simple manner in the powder formulation of the invention accessible to them influencing a continuous release, the profile of which is controllable via the composition of the mixture.

The invention also powder formulations for the controlled, sustained release of active ingredients containing at least two organically modified, inorganic layer compounds, each containing at least one active ingredient and

optionally additives

characterized in that they are obtainable by a manufacturing method in which

each one organically modified layer compound is dispersed in a separate solution of one or more active substances in a solvent or a solvent mixture,

whereby the unmodified inorganic layered compounds on which the at least two organically modified, inorganic layer compounds are based differ, and

the respective solvent or solvent mixture is then separated off,

The use of different at least two organically modified, inorganic layer compounds underlying unmodified inorganic layer compounds with otherwise identical manufacturing steps in the same solvents or solvent mixtures and equipped with the same modifiers in the same composition organically modified inorganic layer compounds causes a different release behavior in the respective resulting layer compound formulation and a mixture of such formulations of individual formulations prepared with various inorganic layered compounds exhibits a slowed, continuous release, the profile of which can be controlled in a surprisingly simple manner by the composition of the mixture.

Likewise provided by the invention are any mixtures of the preferred powder formulations described above.

The powder formulations according to the invention have the advantage that, due to the adjustable release profile, the supply of active ingredient takes place continuously over a relatively long period of time, the leaching and the toxicity are reduced and the odor load is reduced by likewise controlled release of the active ingredient into the gas phase , the photo and Weathering stability of the drug is ensured over a longer period of time and originally crystalline drugs are released amorphous and over a longer period of time, which, for example, the leaf clearance is increased.

The invention also relates to a process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, sustained release of active ingredients, characterized in that

each an organically modified layered compound is dispersed in a separate solution of at least one or more active ingredients in a solvent or a solvent mixture

in which

either the respective solvents or solvent mixtures differ from one another or

the organically modified inorganic layered compounds in at least one modifier or with the same modifiers these differ in their composition ratio or

the respective solvent or solvent mixture is then separated off,

- The respective resulting powder of organically modified layer compound and active ingredient homogenized and

The invention also relates to a further process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, delayed release of active substances, characterized in that

in each case an organically modified layer compound is dispersed in a separate solution of at least one or more active substances in a solvent or a solvent mixture, wherein the respective solvents or solvent mixtures differ from each other and

the respective solvent or solvent mixture is then separated off,

the respective resulting powder of organically modified layer compound and active substance homogenized and

Furthermore, the invention relates to a further process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, delayed release of active substances, characterized in that

in each case an organically modified layer compound is dispersed in a separate solution of at least one or more active substances in a solvent or a solvent mixture,

wherein the organically modified, inorganic layer compounds each carry one or more modifiers and the layer compounds in at least one modifier or with the same modifiers differ in their composition ratio, and

the respective solvent or solvent mixture is then separated off,

in each case an organically modified layer compound is dispersed in a separate solution of at least one or more active substances in a solvent or a solvent mixture, wherein the at least two organically modified, inorganic layer compounds underlying unmodified inorganic layer compounds differ and

the respective solvent or solvent mixture is then separated off,

The inventive method is characterized in that the organically modified layered compound in a solution of the active ingredient in one of the u.g. Solvent or dispersed in a solvent mixture. Alternatively, in a first step, a dispersion of the modified layered silicate and a solution of the active ingredient in the solvent (s) may be prepared and then mixed.

In the context of the invention, "different solvents or solvent mixtures" are understood to mean solvents which differ fundamentally in their chemical structure or when mixed in at least one chemical component and / or in their composition.

In addition, solvent mixtures are understood as meaning those which can be composed over the complete volume fraction, whereby only a miscibility is assumed.

The solvent is separated from the solid after a contact time.

The separation of the solvent can preferably be carried out by filtration of the solid or by centrifugation and separation of the supernatant. In this advantageous embodiment of the method, excess active substance is largely removed. This may be advantageous for formulations in which an initial release should be largely suppressed.

The formulation, after separation of the solvent (s) in another preferred embodiment, may be washed to remove excess active agent adsorbed on the outer surface. As a result, an initial release is suppressed, only at the inner surfaces adsorbed drug, which is released later, contributes to the effect. In a particularly preferred embodiment, the solvent is separated by distillation or evaporation against a vacuum. The advantage of this process is that no active ingredient is lost as a result of the process, since any excess active substance may adhere to the outer surfaces. In addition to the cost aspect, it may be desirable in certain formulations to initially release a certain amount of active ingredient which is increased in comparison with the later release, eg because in the beginning of the germination phase the germs are the most sensitive to pests.

The residual complex of active ingredient and organically modified layered compound is, for example, homogenized by grinding and is mixed with at least one other powder according to the method of claim 10-14.

In a preferred embodiment of the method according to the invention, the powder formulation according to the invention can then also be incorporated into other active ingredient formulations or multicomponent formulations.

The ratio between active ingredient and organically modified layered compound is between 0.01 g and 10 g of active ingredient per g of layered compound, preferably between 0.1 g and 2 g of active ingredient per g of layered compound, more preferably between 0.2 g and 1 g of active ingredient per g of layered compound ,

The concentration of the modified layer compound in the solvent is between 0.01 and 50% by weight, preferably between 0.1 and 30% by weight, more preferably between 1 and 10%. The dispersion can be carried out by means of a simple stirrer, shaker, Ultraturrax, ultrasound, high-pressure homogenization or wet grinding.

The exposure time is between 10 s and 1 week, preferably between 30 min and 48 h, more preferably between 1 h and 12 h. The preparation is carried out at temperatures between 0 ⁰ C and 200 ⁰ C, preferably between 0 ⁰ C and 100 ⁰ C, more preferably between 10 ⁰ C and 70 ⁰ C under atmospheric pressure and may optionally be carried out under reflux.

Unmodified layer compounds which can be used for the mixtures according to the invention are preferably those of the mineral type montmorillonite, as contained as the main constituent in the bentonite, or the bentonite itself. In addition, both synthetic and naturally occurring layer compounds can be used, such as the layered silicates or clay Allevardite, amesite, beidellite, bentonite, fluorhectorite, flur vermiculite, mica, halloysite, hectorite, illite, montmorillonite, muscovite, nontronite, palygorskite, saponite, sepiolite, smectite, stevensite, talc, vermicullite, and synthetic Talcum types and the Alkali silicates maghemite, magadiite, kenyaite, makatite, silinaite, grumantite, revdite and their hydrated forms and the associated crystalline silicas or other inorganic layer compounds such as hydrotalcites, double hydroxides and heteropolyacids, preferably phyllosilicates and double hydroxides.

In the context of the invention, different unmodified inorganic layer compounds are understood as meaning those which differ in their chemical composition and / or their structure.

The cation exchange capacities of the anionic layer compounds are between 10 and 260 meq / 100 g, preferably between 40 and 200 meq / 100g, more preferably between 50 and 150 meq / 100g. The anion exchange capacities of the cationic layer compounds (e.g., hydrotalcites, double hydroxides) are between 0.1 and 4.7 meq / g, preferably between 0.5 and 3 meq / g, more preferably between 0.7 and 2.6 meq / g.

Preferred modifiers of the negatively charged layer compounds are chemical compounds of the alkyl or arylalkyl ammonium or amine or phosphonium type, whose cationic charge is balanced by the anionic layer charges or by excess anions, e.g. Chloride or bromide ions from the original compounds.

Ammonium compounds are understood to mean those of the formula (NR ¹ R ² R ³ R ⁴ ) ⁺ A ^' ,

wherein

R 1, R ^, R ³ and R ⁴ are each independently C _j - C _j g alkyl, optionally interrupted by one or more oxygen atoms interrupted C 2 - C _j g-alkyl, such as 1-10 E- thylenoxideinheiten, Cg - C ^ -Aryl, C5 - C 12-cycloalkyl, where the radicals mentioned in each case by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles may be substituted and / or carry 1-4 double bonds.

R 1, R ² , R ³ and R ⁴ may additionally be hydrogen.

R ^1, R ^2, R ³ and R ⁴ can furthermore C] - C ₁ S -Alkyloyl (alkylcarbonyl), C ₁ - CJg- Alkylo- xycarbonyl, C5-C ₁ 2-cycloalkylcarbonyl or Cg - C ^ -Aryloyl (arylcarbonyl ), where the radicals mentioned may each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.

Optionally C ₁ -C 4 -alkyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, methyl, Ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl , 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1 (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2- Methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3 Hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methyl aminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6- Phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl and

C 2-6 -alkyl optionally interrupted by one or more oxygen atoms, for example for 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl, 1-hydroxy-3,6,9 trioxa undecyl, 7-hydroxy-4-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxa nonyl, 14-hydroxy-5,10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-

Methoxy-3,6-dioxa-octyl, 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-

Methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3- oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 1 l-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8- dioxa undecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

for example, carboxy, carboxamide, hydroxy, di- (C 1 -C 4 -alkyl) -amino, C 1 -C 4 -alkyloxycarbonyl, cyano or C 1 -C 4 -alkyloxy,

^• optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen,

C 1 -C 4 -aryl substituted by heteroatoms and / or heterocycles is, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Diethylphenyl, where propylphenyl, tert-butylphenyl, dodecylphenyl, methoxy xyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,

C 5 -C -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl,

Chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, as well as a saturated or unsaturated bicyclic system, e.g. Norbornyl or norbornenyl,

C 1 -C 4 -alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

C _j - C \ g -Alkyloyl (alkylcarbonyl) is, for example, acetyl, propionyl, n-butyloyl, sec-butyloyl, tert-butyloyl, 2-ethylhexylcarbonyl, decanoyl, dodecanoyl, chloroacetyl, trichloroacetyl or trifluoroacetyl.

C 1 -C 12 -alkyloxycarbonyl is, for example, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, sec-butyloxycarbonyl, tert-butyl oxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl or benzyloxycarbonyl.

C 5 -C 12 -cycloalkylcarbonyl is, for example, cyclopentylcarbonyl, cyclohexylcarbonyl or cyclododecylcarbonyl.

Cg - C _j 2 -Aryloyl (arylcarbonyl) is, for example benzoyl, toluoyl, xyloyl, α-naphthoyl, .beta.-naphthoyl, chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl or trimethylbenzoyl.

R 1, R 2, R 1 and R ⁴ are each independently hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2 (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino and chloro.

Preferably, R ^{4 is} methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, acetyl , Propionyl, t-butyryl, methoxycarbonyl, ethoxycarbonyl or n-butoxycarbonyl. In principle, the same substituents apply to phosphinium ions as described in detail for the ammonium ions.

Particularly preferred phosphonium ions corresponding to formula (PR ¹ R ² R ³ R ⁴ ) * are those in which independently of one another

R ^{4 is} acetyl, methyl, ethyl or n-butyl and

RI, R ² , and R ^ are phenyl, phenoxy, ethoxy and n-butoxy.

Likewise, the ammonium and / or phosphonium ions may be heterocyclic compounds.

Among them, pyridinium and imidazolium ions are preferred.

Very particularly preferred cations are 1,2-dimethylpyridinium, 1-methyl-2-ethylpyridinium, 1-methyl-2-ethyl-6-methylpyridinium, N-methylpyridinium, 1-butyl-2-methylpyridinium, 1-butyl 2-ethylpyridinium, 1-butyl-2-ethyl-6-methylpyridinium, n-butylpyridinium, 1-butyl-4-methylpyridinium, 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-butyl-3-methyl- imidazolium, 1,3,4,5-tetramethylimidazolium, 1,3,4-trimethylimidazolium, 2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 3,4-dimethylimidazolium, 2-ethyl-3, 4-dimethylimidazolium, 3-methyl-2-ethylimidazole, 3-butyl-1-methylimidazolium, 3-butyl-1-ethylimidazolium, 3-butyl-1,2-dimethylimidazolium, 1,3-di-n-butylimidazolium, 3-butyl-1,4,5-trimethylimidazolines, 3-butyl-1,4-dimethylimidazolium, 3-butyl-2-methylimidazolium, 1,3-dibutyl-2-methylimidazolium, 3-butyl-4-methylimidazolium, 3-butyl-2-ethyl-4-methylimidazolium and 3-butyl-2-ethylimidazolium, 1-methyl-3-octylimidazolium, 1-decyl-3-methylimidazolium.

Particularly preferred are 1-butyl-4-methylpyridinium, 1-n-butyl-3-methylimidazolium and 1-n-butyl-3-ethylimidazolium.

As anions A ^' are in principle all anions conceivable.

Preferred anions are halides, F ", Cl", Br ^" , I", acetate CH ₃ COO ^" , trifluoroacetate CF ₃ COO, triflate CF ₃ SO ₃ ", sulfate SO ₄ ² , hydrogen sulfate HSO ₄ ", methyl sulfate CH ₃ OSO ₃ ", ethyl sulfate, C ₂ HSOSO ₃ ^" , sulfite SO ₃ ² ", hydrogen sulfite HSO ₃ ", aluminum chlorides AlCl ₄ ", Al ₂ Cl 7", Al ₃ CliO "'aluminum tetrabromide AlBr ₄ -, nitrite NO ₂ ^" , nitrate NO ₃ ^" , Copper chloride CuCl ₂ ", phosphate PO ₄ ³ ", hydrogen phosphate HPO ₄ ² ", dihydrogen phosphate H ₂ PO ₄ ", carbonate CO ₃ ² ", bicarbonate HCO ₃ "or borates, such as B (OH) ₄ ^' . Preferred modifiers of the positively charged layer compounds (eg double hydroxides, hydrotalcites) are carboxylic acids, sulfonic acids or organic sulfates or their salts with alkyl or arylalkyl radicals.

Preferred are carboxylic acids of the formula (R ¹ R ² R ³ R ⁴ ) C-COO ^' K ⁺ and / or sulfonic acids of the formula (R ¹ R ² R ³ R ^ C-SO ₃ K or organic sulfates of the formula (R ¹ R ² R ³ R 1 CO-SO ₂ -OC (R ¹ R ² R ³ R ⁴ ) wherein

RI, R 2, R 3 _nd R ⁴ are each independently Ci - C ^ g-alkyl, optionally substituted by one or more oxygen atoms interrupted C 2 - Cig-alkyl, such as thylenoxideinheiten 1-10 E-, Cg - CI2 Aryl, C5 - C 12-cycloalkyl, where the radicals mentioned may each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or can carry 1-4 double bonds.

RS R% R ³ and R ⁴ may also be hydrogen.

R ^1, R ^2, R ³ and R ⁴ can furthermore Ci - Ci2-mean aryloyl (arylcarbonyl), wherein - Cj g -Alkyloyl (alkylcarbonyl) Ci - Cj ₈ - alkylene loxycarbonyl, C5-Ci2-Cg cycloalkylcarbonyl, or the radicals mentioned can each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.

Optionally C 1 -C -alkyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1, 3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p Methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2 Butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2 Butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluorom ethyl, 1, 1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6- Methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4- Dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4- Methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl and

optionally interrupted by one or more oxygen atoms interrupted C2 - C _j g alkyl, for example, for 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl, l l-hydroxy-3,6,9-trioxa undecyl, 7-hydroxy-4-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 1-methoxy-3,6,9-trioxa-undecyl, 7 -Methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10 -oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 1-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa heptyl, 1-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl ,

functional groups, for example, for carboxy, carboxamide, hydroxy, di- (C 1 -C 4 -alkyl) -amino, C 1 -C 4 -alkyloxycarbonyl, cyano or Q-C 4 -alkyloxy,

C 1 -C -aryl which is unsubstituted or substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, Dichloφhenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2 , 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl , 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,

optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5 - C [2 "cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl , Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl,

Chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl, C 1 to C 4 -alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

C _j -C 1 -alkyloxy (alkylcarbonyl) is, for example, acetyl, propionyl, n-butyloyl, sec-butyloyl, tert-butyloyl, 2-ethylhexylcarbonyl, decanoyl, dodecanoyl, chloroacetyl, trichloroacetyl or trifluoroacetyl.

C 1 -C 9 -alkyloxycarbonyl is, for example, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, sec-butyloxycarbonyl, tert-butyl-oxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl or benzyloxycarbonyl.

C 3 -C 12 -Aryloyl (arylcarbonyl) is, for example, benzoyl, toluyl, xyloyl, α-naphthoyl, β-naphthoyl, chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl or trimethylbenzoyl.

R, R 1, R 1 and R ⁴ independently of one another preferably represent hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino and chloro.

Preferably, R ^{4 is} methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, acetyl , Propionyl, t-butyryl, methoxycarbonyl, ethoxycarbonyl or n-butoxycarbonyl.

K stands for any cation, preferably for the ions of the alkali metals or alkaline earth metals or for ammonium. K is more preferably H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Cu ²⁺ , Zn ²⁺ Fe ²⁺ , Fe ³⁺ , Mn ²⁺ and NH ₄ ⁺ . The cations can be free or complexed.

The surface charges of the layer compounds are compensated in a preferred embodiment, between 10 and 200%, preferably between 70 and 130%, particularly preferably between 90 and 110%, which corresponds to the occupancy rate of the surface.

The occupation of the surface can - depending on the application - completely or only partially. In a preferred embodiment of the invention, the unoccupied part of the inorganic layer compound can still act as a water reservoir or mineral salt dispenser when partially occupied, and the formulation is generally more water-wettable. In a further preferred embodiment, an approximately complete coverage advantageously results in formulations which contain further organic additives such as, for example, adhesives. The anionic layer compounds are modified in a manner known to those skilled in the art, for example by the action of an aqueous solution or of polar organic solutions of the ammonium or phosphonium compounds on a dispersion of the unmodified layer compounds (Lagaly, G., reactions of the clay minerals. Steinkopff Verlag, Darmstadt, 1993.). Such ammonium or phosphonium compounds are used between 0, 1 and 2 times the cation exchange capacity (CEC), preferably between 0.3 and 1.5 times CEC, more preferably between 0.4 and 1.2 times CEC. In addition, mixtures of at least two of the above modifiers can be used. The mixtures can be reacted in a one-pot reaction with the layer compound or else sequentially with one modifier in the appropriate solvent or solvent mixture successively, with a partial occupancy first between 1% and 99% of the CEC with one modifier, then another Occupancy between 1% and 99% of the CEC with the next modifier, etc. until full occupancy. In this way, several modifiers can be applied.

The modification of the cationic layer compounds is carried out correspondingly, for example, by the action of an aqueous solution or solutions in polar organic solvents of carboxylic acids, sulfonic acids or sulfates or their salts on aqueous dispersions or dispersions in polar solvents of the cationic layer compounds or other common processes (Rives, Vol. V., Layered Double Hydroxides: present and future, Nova Science Publishers Inc., New York, 2001). The carboxylic acids, sulfonic acids or sulfates are used between 0.1 and 2 times the anion exchange capacity, preferably between 0.7 and 1.3 times the anion exchange capacity. In addition, mixtures of at least two of the above-mentioned. Modifiers are used. In this case, the mixtures can be reacted in a one-pot reaction with the layered compound or else, as described above, sequentially with one modifier in each case in the solvent or solvent mixture suitable for this purpose.

The layered compounds may be specially modified or commercially available products of the types Cloisite (Southern Clay Products Inc.), Nanofil (South Chemistry), Nomer (Nanocor Inc.), etc. may also be used. Nanofil 15 (distearyldimethylammonium montmorillonite, Südchemie), Nanofil 32 (stearylbenzyldimethylammonium montmorillonite, Südchemie), Nanofil 757 (sodium montmorillonite, Süchemie), Nanofil 784 (amododecanoic acid montmorillonite, Südchemie), Nanofil 804 (stearyldiethoxyamine Montmorillonite), Nanomer I30E (octadecylamine montmorillonite, Nanocor, Inc), Nanomer I.24T (amododecanoic acid montmorillonite, Nanocor, Inc.), and Nanomer Unmodified Clay (Nanocor, Inc.). preferably used. The active substances which can be used in the mixtures according to the invention may be, for example but not limited to, all substances customary for plant treatment, preferably fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, plant nutrients, and attractants or repellents.

Examples of fungicides include:

2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-Dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl (E) -2- {2- [6- (2-cyanophenoxy) -pyrimidin-4-yloxy] -phenyl} -3-methoxyacrylate; Methyl (E) -methoximino [alpha- (o-tolyloxy) -o-tolyl] -acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthobiobate, calcium polysulfide, captafol, captan, carbendazim, carboxin , Quinomethionate (quinomethionate), chloroneb, chloropierine, chlorothalonil, cholinezolate, cufraneb, cymoxanil, cyproconazole, cyprofuram, carpropamide, dichlorophene, diclobutrazole, dichlofluanid, diclomethine, diclorane, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, Dinocap, diphenylamine, dipyrrithione, ditalimfos, dithianone, dodine, drazoxolone, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfurur, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentinhydroxyd, ferbam, ferimzone, fluazinam, fludioxonil, Fluoromides, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminum, Fthalide, Fuberidazole, Furalaxyl, Furmecyclox, Fenhexamid, Guazatine, hexachlorobenzene, hexaconazole, hymexazole, imiazalil, imibenconazole, iminoctadine, Iprobenfos (IBP), iprodione, isoprothiolane, iprovalicarb, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture , Mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, mycollanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron , Phosphodiphene, pimaricin, piperaline, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozen (PCNB), quinoxyfen, sulfur and sulfur preparations, spiroxamine, tebuconazole, tecloftalam, Tecnazene, tetraconazole, thiebendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, tri azoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole, trifloxystrobin, validamycin A ₅ vinclozoline, zineb, ziram, and 2- [2- (1-chloro-cyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [l, 2,4] triazole-3-thione. As examples of bactericides may be mentioned:

Bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Examples of insecticides, acaricides and nematicides include:

Abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, A-vermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, bacillus thuringiensis, 4-bromo-2- (4-chlorophenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -1H-py? ol-3-carbonitriles, benzodecarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, bofenprox, bromophos A, bufencarb, buprofezin, butocarboxine, butylpyridaben, cadusafos, carbaryl, carbofuran , Carbophenothione, carbosulfan, cartap, chloethocarb, chloroetoxyfos, chlorfenvinphos, chlorofluorotrone, chlormephos, N-Kό-chloro-S-pyridinyl-methyl-N'-cyano-N-methyl-ethanimidamide, chlorpyrifos, chloφyrifos M, cis-resmethrin, clocythrin, clofentezine, clothianidin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthione, Dichlorvos, dicliphos, dicrotophos, diethione, diflubenzuron, dimethoate, dimethylv inphos, dioxathione, disulfotone, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthione, fenvalerate, fipronil, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda cyhalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulphphos, metaldehyde, methacrifos, methamidophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyram, omethoate, oxamyl, oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethrin, Phenthoate, Phorat, Phosalone, Phosmet, Phosphamidone, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb , Propaphos, Propoxur, Prothiophos, Prothoate, Pymetrozine, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos , Terbam, terbufos, tetrachlorovirphos, thiacloprid, thiafenox, thiamethoxam, thiodicarb, thiofanox, thiomethone, thionazine, thuringiensin, tralomethrin, transfluthrin, triarathene, triazophos, triazuron, trichlorofon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin , Imidacloprid, thiacopride, thiamethoxam, acetamiprid, clothianidin, betacyfluthrin, cypermethrin, transfluthrin, lambda-cyhalothrin and / or azinphosmethyl are particularly preferably contained in the powder formulations according to the invention.

Examples of herbicides include:

Anilides, e.g. Diflufenican and propanil; Arylcarboxylic acids, such as e.g. Dichloro-picolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxyphenoxy-alkanoic acid esters, e.g. Diclofop-methyl, fenoxapropethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, such as Chloridazon and norflurazon; Carbamates, such as e.g. Chlorpropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g. Acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as e.g. Chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines, such as e.g. Alloxydim, clethodim, cycloxydim, ethoxydim and tralkoxydim; Imidazolinones, e.g. Imazethapyr, Imazamethabenz, Imazapyr and Imazaquin; Nitriles, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. mefenacet; Sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuronethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiolcarbamates, e.g. Butylates, cyclates, dialkylates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g. Atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, e.g. Aminotriazole, benfuresates, bentazones, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesates, fluorochloridones, glufosinates, glyphosates, isoxaben, pyridates, quinchlorac, quinmerac, sulphosates and tridiphanes. Furthermore, 4-amino-N- (1,1-dimethylethyl) -4,5-dihydro-3- (1-methylethyl) -5-oxo-1H-1, 2,4-triazole-1-carboxamide and benzoic acid , 2 - ((((4,5-dihydro-4-methyl-5-oxo-3-propoxy-1H-1,2,4-triazol-1-yl) carbonyl) -amino) -sulfonyl) -methyl ester.

Particular preference is given to containing propoxycarbazone sodium, flucarbazone sodium, amicarbazone dichlobenil and / or phenyluracil in the powder formulations according to the invention.

As examples of plant growth regulators chlorocholine chloride and ethephon may be mentioned.

Examples of plant nutrients include common inorganic or organic fertilizers for the supply of plants with macro and / or micronutrients. Examples of repellents include diethyl tolylamide, ethylhexanediol, 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -l-methylpropyl ester (Bayrepel®) and butyrolactone.

In a further preferred embodiment, it is possible to formulate pharmacological, veterinary-medicinal cosmetic active ingredients, such as aromas or fragrances, or material protection-relevant active substances in which a linearized release profile with a continuous release of active ingredient is desired.

Suitable solvents for the active compounds in the process according to the invention or as dispersants for the layer compounds are all customary solvents or solvent mixtures in the conceivable mixing ratios. These solvents or solvent mixtures swell the organically modified phyllosilicates to different extents. Solvents can be:

Hydrocarbons or mixtures thereof (C5 - Cl 8), such as n-pentane, n-hexane, n-heptane, n-octane, petroleum ether.

Halogenated hydrocarbons such as mono-, di-, tri-, tetra-chlorocarbon, preferably dichloromethane and chloroform, ethers - e.g. Diethyl ether, glycol dimer, esters - such as propylene glycol monomethyl ether acetate, dibutyl adipate, ethyl acetate, hexyl acetate, heptyl acetate, tri-n-butyl citric acid, diethyl phthalate and di-n-butyl phthalate "ketones - e.g. Acetone, methyl isobutyl ketone and cyclohexanone, alcohols such as methanol, ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and l-methoxy-2-propanol, or combinations thereof; Amides - such as: B. Dimethylformamide or dimethylacetamide, in addition strongly polar solvents such as DMSO, furthermore cyclic compounds such as N-methyl-pyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone, N-octyl-caprolactam, N-dodecyl-caprolactam and γ-butyrolactone or cyclic mono- or diethers such as THF and dioxane, nitriles such as acetonitrile, furthermore aromatic hydrocarbons such as xyxlol, toluene, benzene, nitrophenol. In addition, water can also be used as diluent.

These same solvents can also be used for further formulation of the powder formulations according to the invention.

The powder formulations according to the invention can be used as such or after addition of further formulation auxiliaries for the application of agrochemical active compounds in crop protection both in agriculture and forestry as well as in horticulture. Suitable formulation auxiliaries are all customary components which can be used in plant treatment compositions, for example dyes, wetting agents, dispersants, emulsifiers, defoamers, Preservatives, drying-delaying components, antifreezes, secondary thickeners, solvents and, in the case of the preparation of mordants, also adhesives or polymeric binders.

Dyes which can be used for further preparation of the powders according to the invention as plant treatment agents are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, CI. Pigment Red 112 and CI. Solvent Red 1 known dyes.

Suitable wetting agents which can be used to formulate the powders according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds. Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.

Suitable dispersants and / or emulsifiers which can be used for formulating the powders according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds. Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Particular suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.

Suitable defoamers which can be used for formulating the powders according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds. Preferably usable are silicone defoamers and magnesium stearate.

Suitable preservatives which can be used to formulate the powders according to the invention are all substances customary for such purposes for the formulation of agrochemical active substances. Examples include dichlorophen and benzyl alcohol hemiformal.

Suitable drying-delaying components and antifreeze agents which can be used to formulate the powders according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to polyhydric alcohols, such as glycerol, ethanediol, propanediol and polyethylene glycols of various molecular weights. As secondary thickening agents which can be used for formulating the powders according to the invention, all substances which can be used for such purposes in agrochemical compositions are suitable. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, and finely divided silica.

Likewise provided by the invention is the use of the powder formulations according to the invention as a seed dressing.

Adhesives are then used to formulate the powders according to the invention as mordants. As such, all customary usable in pickling binders come into question.

Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, biodegradable polymers such as polylactides, collagen, gelatin, cellulose and cellulose derivatives, starch and derivatives thereof and Tylose.

Particularly preferred adhesives are dispersions of biodegradable polyester polyurethane polyureas in water. Such dispersions are known (see WO 01-17347).

The powder formulations according to the invention can be used as such or even after mixing with further formulation auxiliaries and / or plant treatment agents and, if appropriate, further diluting with water in practice. The application is carried out by conventional methods, so for example by scattering, pouring, spraying or spraying.

Another object of the invention is the use of powder formulations according to the invention in a spray application. The adsorption of crystalline active substances in the amorphous state prevents recrystallization and thereby promotes leaf penetration.

The invention is explained in more detail below with reference to the following examples without, however, limiting them to these.

It shows:

1 shows the schematic structure of the measuring apparatus used for the release experiments (carried out according to Example 10),

2 shows the plot of the released amount of active ingredient imidachloprid F in% of active ingredient formulations prepared from various solvents from Example 2 (b., Water, c., Acetone, n-heptane, e. ethanol) and their mixture (a.) Example 6 with pure imidachloprid as reference (for crystalline imidacloprid) plotted against time t, 3 shows the plot of the released amount of active ingredient imidachloprid F in% of active compound formulations of Example 4 prepared in various ethanol / toluene mixing ratios against the time t (a 100% ethanol, b 80% ethanol, c 50% ethanol, 20% ethanol, 0% ethanol),

4 shows the application of the released amount of active ingredient imidachloprid F in% of active ingredient formulations of Example 5 prepared from various modified sheet silicates in ethanol (a Nanofil 15, b, Nanofil 784, c, Nanomer I30E, that is Nanofil 32, e 804, f Nanomer sodium form, g.Nanofil 757, h.Nanomer I24T) and their mixture from Example 7 (J.Mixture) plotted against time t and

5 shows the application of the released amount of active ingredient imidachloprid F in% from rice stain prepared according to Example 8 from an active ingredient formulation prepared according to Example 1 and Example 2 in ethanol (b) rice stain layered silicate formulation from ethanol) and from rice stain prepared according to Example 9 from according to Example 6 prepared active ingredient formulation mixture (c., rice stain layered silicate formulation mixture) with pure imidachopride rice stain (a.Russbeize Imidacloprid) as reference plotted against time t.

Examples

Nanosil 15 (distearyldimethylammonium montmorillonite, Südchemie), Nanofil 32 (stearylbenzyldimethylammonium montmorillonite, Südchemie), Nanofil 757 (sodium montmorillonite, Süchemie), Nanofil 784 (aminododecanoic acid montmorillonite, Südchemie), Nanofil 804 ( Stearyldiethoxyamine montmorillonite), Nanomer I.30E (octadecylamine montmorillonite, Nanocor, Inc), Nanomer I.24T (aminododecanoic acid montmorillonite, Nanocor, Inc.), and Nanomer Unmodified Clay (Nanocor, Inc.) ,

Example 1: Preparation of organic phyllosilicate dispersions

In order to prepare a layered silicate in organic solvent modified by about 1% by weight, 5 g of nanomer I.30E (Nanocore Inc.) in 500 g of solvent were stirred at 20,500 rpm using an UltraTurrax stirrer (TuraxT25 S25N-18G) The dispersions were shaken overnight (about 15 h) on a laboratory shaker (150 rpm, RT). Accordingly, dispersions were prepared in the following solvents: water, n-heptane, DMSO, acetone, ethanol, toluene.

Example 2: Drug formulation via layered silicate solvent dispersions

The dispersions from Example 1 were then admixed with 200 mg of IMIDACLOPRID. The dispersions were shaken overnight on a shaker at RT and then evaporated on a rotary evaporator at 45 ⁰ C to dryness (mbar 25, 5-7 days) in a vacuum drying cabinet at 55 ° C post-dried and on a vibratory mill at 30 Hz for 5 minutes in 25 ml PE cups ground with two ZrO ₂ grinding beads (d = 10mm).

The release behavior was analyzed according to Example 10. The result is shown in Fig. 2 (b., Water, c., Acetone, n-heptane, e., Ethanol and their mixture (a.) Of Example 6).

Example 3: Preparation of organic phyllosilicate dispersions in solvent mixtures

Formulations were prepared in solvent mixtures of ethanol and toluene in different mass fractions. The solvents were mixed in the following ratios of ethanol / toluene:

• w (EtOH) = 0 396 g toluene + 0 g ethanol

• w (EtOH) = 0.2 316.8 g toluene + 179.2 g ethanol

• w (EtOH) = 0.5 198.0 g toluene + 198.0 g ethanol • w (EtOH) = 0.8 79.2 g toluene + 316.8 g ethanol

• w (EtOH) = 1 g toluene + 396 g ethanol

In each solution, 4 g of Nanomer I.30E were dispersed (1 min in Ultraturrax at 20500 U / min). The dispersions were shaken overnight on the laboratory shaker (150 rpm, RT).

Example 4: Drug formulations over layered silicate-solvent mixture dispersions

The dispersions from Example 3 were then admixed with 160 mg of IMID ACLOPRID and prepared in accordance with Example 2 powdery formulations. The release behavior was analyzed according to Example 10. The result is shown in Fig. 3 (a, 100% ethanol, b, 80% ethanol, c, 50% ethanol, i.e., 20% ethanol, e, 0% ethanol).

Example 5: Drug formulations based on differently modified phyllosilicates

According to Example 2 powder formulations were prepared based on differently modified layered silicates. In several 50OmL glass bottles each 396g of ethanol were filled. In each solution, 4 g of phyllosilicate were dispersed (1 min in Ultraturrax at 20500U / min). Nanosil 15 (distearyldimethylammonium montmorillonite, Südchemie), Nanofil 32 (stearylbenzyldimethylammonium montmorillonite, Südchemie), Nanofil 757 (sodium montmorillonite, Süchemie), Nanofil 784 (aminododecanoic acid montmorillonite, Südchemie), Nanofil 804 (stearyldiethoxyamine-montmorillonite) were used as layer silicates. , Nanomer I.30E (octadecylamine montmorillonite, Nanocor, Inc), nanomer I.24T (aminododecanoic acid montmorillonite, Nanocor, Inc.), and Nanomer Unmodified Clay (sodium montmorillonite, Nanocor, Inc.).

The dispersions were shaken overnight on the laboratory shaker (150 rpm, RT), then each 160 mg of IMID ACLOPRID were added, dispersed (30 sec in Ultraturrax at 20500U / min) and the dispersions shaken overnight on the laboratory shaker (150 rpm, RT ). Then the dispersions were concentrated in a rotary evaporator at 45 ° C and then dried in a vacuum oven (at <10mbar & 40 ⁰ C). The dried samples were ground on a vibratory mill at 30Hz for 5min with two ZrO ₂ grinding beads (d = 10mm).

The release behavior was carried out according to Example 10. The result is shown in Fig. 4 (a, nano-film 15, b, nano-film 784, c, nanoomer I30E, d., Nanofil 32, e, nanofil 804, f, nanomer sodium form, g, nanofil 757, h, nanomer I24T, j Mixture) Example 6: Mixtures from Example 2

Powder formulations from example 2 were mixed. For this purpose, in each case 300 mg of the pulverulent formulations originally prepared from acetone, DMSO, ethanol and n-heptane and 30 mg of the pulverulent formulation prepared from water were mixed in an agate mortar and the release was measured in accordance with Example 10. The result is shown in Fig. 2 (b., Water, c., Acetone, n-heptane, e., Ethanol and their mixture (a.)).

Example 7: Mixtures from Example 5

Powder formulations from example 5 were mixed. For this purpose, approximately 250 mg of imidaclide-clay powder formulations (4% by weight of IMID ACLOPRID per g of clay) based on nanomer 1.30 E, Nanofil 15, Nanofil 32, Nanofil 757 were mixed, homogenized in an agate mortar and homogenized in each release cell transferred a mixture mass of about 260 mg. The release was measured according to Example 10. The result is shown in Fig. 4 (a) nanofilts 15, b, nanofilts 784, c, nanomer I30E, i.e. nanofil 32, e, nanofil 804, f, nanomer sodium form, g, nanofil 757, hananomer I24T, j. Mixture) as a "mixture".

Example 8 Release from a Rice Stain (Clay Formulation from Ethanol)

In 6 g of water / ethanol mixture (1: 1) were 1 g Nanomer I30.E - Imidacloprid mixture (10 wt .-% imidacloprid per g of clay, prepared according to Example 1 or Example 2 from ethanol) for 10 min dispersed with a magnetic stirrer. Subsequently, 0.052 g of the adhesive Impranil DLN Dispersion W 50 (about 50% by weight, from Bayer Material Science) and 0.5112 g of the dye dispersion Levanyl Red BB-LF (1% by weight, from LanXess) were added. This dispersion was shaken vigorously. The result was a highly viscous suspension.

3.7 g of this suspension were mixed in a small beaker with 12 g of rice with the aid of a spatula until the red suspension optically adhered to the rice grains. Thereafter, the pickled rice was stored for about 42 h in a drying oven at 4O ⁰ C. Subsequently, about 3.1 g of the dried rice stain was introduced into each release cell.

As a comparative sample, a rice stain was additionally prepared as indicated above, in which pure imidacloprid was present instead of the phyllosilicate formulation. 93.5 mg imidacloprid were weighed in place of the nanomer I30.E-imidacloprid mixture. In the release experiments, about 2.3 g per release cell of this comparative formulation was used to obtain the same amount of imidacloprid as in the layered silicate formulation.

The release from the layered silicate formulation was significantly delayed. The release was measured according to Example 10. The result is shown in Fig. 5 (a, Reisbeize Imidacloprid, b.Rice dressing phyllosilicate formulation of ethanol, c., Rice dressing layered silicate formulation mixture) as "rice stain layered silicate formulation of ethanol".

Example 9 Release from a Rice Stretcher (Mixture) A rice mordant was prepared starting from a mixture of layered silicate-imidacloprid powders from Example 6 (prepared from the solvents acetone, DMSO, ethanol, toluene, n-hexane) according to Example 8. The release was measured according to Example 10. The result is shown in Fig. 5 (a, Reisbeize Imidacloprid, b.Rice dressing phyllosilicate formulation from ethanol, c., Rice stain layered silicate formulation mixture) as a "rice stain layered silicate formulation mixture." As a comparison, a rice stain with pure IMIDACLOPRID was prepared as in Example 8 in Fig. 5 (a, Reisbeize imidacloprid, b, rice stain, phyllosilicate formulation of ethanol, c, rice stain, layered silicate formulation mixture) are shown as "rice stain imidacloprid".

Example 10: Release Measurements: Description of Flow Measurements

Approximately 260 mg of pulverulent formulation were homogeneously applied in a flow cell to a glass fiber prefilter (Millipore), including a filter made of cellulose ester (0.1 μm, diameter 47 mm, from Millipore) and sealed (see FIG. 1, no. 4) ). For comparability of the samples, the same ratios of imidacloprid / clay and the same absolute amounts of imidacloprid were used in the release measurements. The material of the release cells was polycarbonate, Tygon LFL tubing (diameter 2.2 mm, wall thickness 0.84 mm). The release cells were perfused with a flow of deionized water (Millipore) of 4 ml / min in the flow-through mode (see Fig. 1, No. 9 + 11).

5 μl sample volume was taken automatically at 5 min intervals for single determinations and 15 mins for parallel triplicate determinations (see Fig. 1, Nos. 6 + 7) and in the HPLC (Hewlett Packard 1050, see Fig. 1, No. 8). injected. The separation took place via a separating column Lichrospher® 100RP8 (5 μm, Lycrocart® 125-4). The solvent mixture used was acetonitrile / water, a gradient (10% ACN / 90% H ₂ O pH 2, after 2 min 90% ACN / 10% H ₂ O pH 2) at a flow rate of 1.5 ml / was driven min. The detection was carried out by means of a variable wavelength detector at a wavelength of 282 nm. The analysis time was 3.5 min with 1.5 min post-time. The released concentrations were taken from calibration curves and cumulatively plotted against time. The release between two measurement points was assumed to be linear. This assumption was made by extraction of the residual formulation after termination the flow measurements are checked by a mass balance (estimation of whether a burst between two measuring points distorts the mass balance).

reference numeral

I. Telab ^® BF 414 Diaphragm Pump 2. Julabo Cryostat

3. Thermostatic circuit (RT)

4. Release flow cell with sample

5. Flow tank (VA steel, own construction)

6. HPLC injection needle 7. HPLC autosampler

8. HPLC with Variable Wavelength Detector

9. Water cycle (reflux mode)

10. Pretreatment container for the release agent (e.g., deionized water)

I I. Waste (flow mode)

Claims

claims

1. Containing powder formulations for controlled, sustained release of active ingredients

optionally additives

characterized in that they are obtainable by a manufacturing method in which

in each case an organically modified layer compound is dispersed in a separate solution of one or more active substances in a solvent or a solvent mixture,

in which

either the respective solvents or solvent mixtures differ from one another or

the organically modified inorganic layered compounds in at least one modifier or with the same modifiers these differed in their composition ratio, or

- The respective solvent or solvent mixture is then separated,

the respective resulting powders from the different Lösungsmittelbzw. Solvent mixture approaches are mixed together.

2. Powder formulations for the controlled, sustained release of active substances according to claim 1 containing

at least two organically modified, inorganic layer compounds, each containing at least one active ingredient and optionally additives

characterized in that they are obtainable by a manufacturing method in which

in each case an organically modified layer compound is dispersed in a separate solution of at least one active substance in a solvent or a solvent mixture,

wherein the respective solvents or solvent mixtures differ from each other and

the respective solvent or solvent mixture is then separated off,

3. Powder formulations for the controlled sustained release of active substances according to claims 1 or 2 comprising

- At least two organically modified, inorganic layer compounds, each containing at least one active ingredient and

optionally additives

characterized in that they are obtainable by a manufacturing method in which

wherein the organically modified, inorganic layer compounds each carry one or more modifiers and the layer compounds in at least one modifier or with the same modifiers these differ in their composition ratio, and

the respective solvent or solvent mixture is then separated off,

the resulting powder of organically modified layer compound and active ingredient is homogenized and the respective resulting powders from the different Lösungsmittelbzw. Solvent mixture approaches are mixed together.

4. Powder formulations for the controlled, sustained release of active ingredients according to one of the preceding claims containing

optionally additives

characterized in that they are obtainable by a manufacturing method in which

wherein the at least two organically modified, inorganic layer compounds underlying unmodified inorganic layer compounds differ and

- The respective solvent or solvent mixture is then separated,

the respective resulting powders from the different Lösungsmittelbzw. Solvent mixture approaches are mixed together

5. Powder formulations, characterized in that they are mixtures of powder formulations of claims 1, 2, 3 or 4.

6. Powder formulations according to one of the preceding claims, characterized in that it is the layer compounds are organically modified phyllosilicates or organically modified double hydroxides.

7. Powder formulations according to one of the preceding claims, characterized in that the active substances are agrochemical active substances.

8. Powder formulations according to one of the preceding claims, characterized in that the anionic inorganic layer compounds are those having a cation exchange capacity between 10 and 260 meq / 100 g.

9. Powder formulations according to one of the preceding claims, characterized in that the cationic inorganic layer compounds are those having an anion exchange capacity of between 0.1 and 4.7 meq / g

10. A process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, sustained release of active ingredients, characterized in that

in which

either the respective solvents or solvent mixtures differ from one another or

the organically modified inorganic layered compounds in at least one modifier or with the same modifiers differed in their compositional ratio or

the unmodified inorganic layered compounds on which the at least two organically modified, inorganic layer compounds are based differ, and

the respective solvent or solvent mixture is then separated off,

the respective resulting powder of organically modified layer compound and active ingredient homogenized and

- The respective resulting powder from the different Lösungsbzw. Solvent mixture approaches are mixed together.

11. A process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, sustained release of active substances according to claim 10, characterized in that in each case an organically modified layer compound is dispersed in a separate solution of at least one or more active substances in a solvent or a solvent mixture,

wherein the respective solvents or solvent mixtures differ from one another and

the respective solvent or solvent mixture is then separated off,

12. A process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, sustained release of active substances according to claim 10-11, characterized in that

each an organically modified layered compound in its own solution of at least one or more active substances in a solvent or a

Solvent mixture is dispersed,

the respective solvent or solvent mixture is then separated off,

13. A process for the preparation of formulations based on organically modified inorganic layer compounds for the controlled, sustained release of active substances according to claim 10-12, characterized in that in each case an organically modified layer compound is dispersed in a separate solution of at least one or more active substances in a solvent or a solvent mixture,

the respective solvent or solvent mixture is then separated off,

14. The method according to any one of the preceding claims 10 -13, characterized in that the ratio between active ingredient and organically modified layer compound between 0.01 g and 10 g of active ingredient per g of layered compound.

15. Use of a powder formulation according to one of the preceding claims in seed dressing or as an ingredient in spray mixtures.

16. Use of a powder formulation according to one of the preceding claims in agrochemical, material protection-relevant, pharmaceutical, veterinary-medical or cosmetic formulations.