EP1851262A1

EP1851262A1 - Polymer compositions and their use in the production of active or effective ingredient compositions

Info

Publication number: EP1851262A1
Application number: EP06706746A
Authority: EP
Inventors: Günter OETTER; Christian Krüger; Norbert Wagner; Matthias Bratz; Rainer Berghaus; Peter Dombo
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-02-09
Filing date: 2006-02-08
Publication date: 2007-11-07
Also published as: IL185096A0; CN101151291A; EA200701622A1; JP4635056B2; JP2008530259A; BRPI0606926A2; CN101151291B; KR20070110288A; AR053126A1; CA2596818A1; CR9289A; MX2007009076A; EA014939B1; WO2006084680A1; US20080167189A1; AU2006212414A1

Abstract

The invention relates to polymer compositions, to a method for producing the same and to their use in the production of aqueous active ingredient compositions of water-insoluble active ingredients, especially of active ingredients for use in plant protection.

Description

Polymer compositions and their use for the preparation of active or effect compositions

description

The present invention relates to novel polymer compositions, to a process for their preparation and to their use for stabilizing water-insoluble or sparingly soluble active or effect substances in an aqueous phase and for producing active ingredient compositions of water-insoluble active substances or active substances, in particular of active substances for plant protection.

Active ingredients, d. H. Substances which can already have a physiological effect even in low concentrations are often formulated or used in the form of aqueous active substance compositions. Thus, for example, in the plant protection agent, the active ingredients used for pest control, d. H. Insecticides, fungicides and herbicides, but also growth regulators, often as concentrates, e.g. aqueous concentrates, such as suspensions or emulsions, but also as solid concentrates, such as powders, dusts or granules, formulated and sold, which are diluted to the desired application concentration before they are used by adding a large amount of water (so-called "spray mixture") For pharmaceutically and cosmetically active substances as well as for food additives, for example vitamins, provitamins, etc., aqueous active substance compositions have proven useful, The same applies to the formulation of effect substances, ie low molecular weight compounds which develop a defined technical effect even at a low application rate, eg B. Dyes and UV stabilizers.

A fundamental problem with aqueous active ingredient compositions is that in the

Usually low water solubility of the active ingredients, often less than 10 g / l at

23 ° C / 1013 mbar. Aqueous formulations of such active ingredients and also aqueous ready-to-use preparations are therefore heterogeneous systems, wherein the active ingredient is present as an emulsified or dispersed phase in a continuous aqueous phase. To stabilize these intrinsically metastable systems, emulsifiers or dispersants are usually used. However, their stabilizing effect is often unsatisfactory, so that deposition of the active ingredient, for example creaming or sedimentation of the active ingredient may occur, especially if the aqueous formulation is left for a prolonged period at elevated temperature and / or at strongly changing temperatures or in the vicinity of freezing is stored. This problem is particularly pronounced when the drug tends to crystallize. Often it also comes to the deposition of solid Drug particles when a formulation containing the active ingredient in concentrated form is diluted with water.

Frequently, organic solvents are used to prepare formulations of water-insoluble active ingredients. Thus, one often uses water-miscible solvents as solubilizers, d. H. to increase the solubility of the active or effect substance in the aqueous phase. In turn, water-immiscible solvents serve to convert a solid active ingredient at the application temperature into a liquid phase which is then easier to emulsify. In contrast to suspensions of the solid active substance, the active substance in the solvent droplets is molecularly dissolved in the emulsions and is therefore more readily available on application and therefore more effective. However, the use of relatively large amounts of organic solvents is undesirable due to the known VOC prob- tematics for reasons of occupational hygiene, environmental aspects and in part also for toxicological reasons.

Another disadvantage of conventional aqueous active substance compositions is the comparatively large particle size of the active substance particles or active substance droplets suspended or emulsified in the aqueous phase, which is generally several μm. However, aqueous formulations in which the active ingredient is in finely divided form or is converted into a finely divided form on dilution with water in order to ensure a uniform distribution in the formulation and thus better handling and meterability, and at the same time, are desirable to increase the bioavailability of the active ingredient in the formulation or in the ready-to-use composition. Desirable are formulations which, when diluted with water, provide an active ingredient composition in which the phase containing the active ingredient has mean particle sizes below 500 nm and in particular below 300 nm.

There have been various proposals for the use of amphiphilic block copolymers for the solubilization of water-insoluble drugs in an aqueous vehicle. The term "solubilization" denotes a stable uniform distribution of the water-insoluble active or effect substance in the aqueous phase achieved using solubility-promoting substances (adjuvants), the particles of the disperse phase of active substance often being so small that they scarcely absorb visible light As a result, the amphiphilic block copolymers generally have at least one hydrophilic polymer block and at least one hydrophobic polymer block. For example, US 2003/0009004 proposes for this purpose amphiphilic block copolymers comprising a hydrophilic polyethylenimine block and a hydrophobic block of biodegradable aliphatic polyester. A disadvantage, however, is that comparatively large amounts of polymer, based on the active substance, are required in order to obtain stable aqueous active substance compositions.

US 2003/0157170 describes anhydrous drug compositions containing an amphiphilic diblock copolymer with a polyester as a hydrophobic ingredient and an additive. The compositions form medicated micelles when diluted with water. Another disadvantage here is that comparatively large amounts of polymer are needed to stabilize the active ingredient in the aqueous phase.

WO 02/82900 describes the use of amphiphilic block copolymers for the preparation of aqueous suspensions of water-insoluble crop protection active ingredients. The block copolymers used are prepared by "living" or "controlled" radical block copolymerization of ethylenically unsaturated monomers. Apart from the fact that such processes are comparatively complicated, the aqueous active substance formulations contain relatively large amounts of water-soluble organic solvents. In addition, the process requires the use of toxic transition metal catalysts that remain in the product. In addition, the block copolymers tend to brown.

In summary, despite the principal advantages that block copolymers have for the formulation of water-insoluble active ingredients, the block copolymers known in the art are not fully satisfactory, whether their preparation is very complicated, the stability of the aqueous Drug formulations or drug treatments is unsatisfactory, the activity of the active ingredients is adversely affected or large amounts of polymer, which are lent to stabilize the active ingredient in the aqueous Phanse lent, which may be disadvantageous in addition to increased costs even with the use of such preparations.

The present invention is therefore based on the object to provide substances which allow effective solubilization of water-insoluble active ingredients in an aqueous medium. These substances should be suitable for the preparation of formulations which allow effective stabilization of the active ingredient in the aqueous phase. In particular, these substances should also be suitable for providing aqueous active substance compositions of water-insoluble active ingredients which have no or only a very low content of volatile organic substances. Furthermore, a high stability of using aqueous compositions of these substances prepared in view of separation processes during long storage, with the addition of electrolyte and dilution with water desirable.

This object is surprisingly achieved by a polymer composition obtainable by reaction

a) at least one polymer P1 which carries isocyanate-reactive functional groups R 1 and which is composed of ethylenically unsaturated monomers M 1, wherein the monomers M 1 more than 20 wt .-%, based on the

Total amount of monomers M1, monomers M1a comprising at least one functional group FG selected from tertiary amino groups, imino groups, carboxyamide groups, nitrile groups, lactam groups, keto groups, aldehyde groups, urea groups, polyether groups, carboxyl groups, sulfonyl groups, hydroxysulfonyl groups and sulfonamide groups is

b) at least one poly-C ₂ -C ₄ -alkylene ether P2 carrying isocyanate-reactive functional groups R ₂ ,

c) having at least one isocyanate group-containing compound V, which has a functionality of at least 1, 5 with respect to the isocyanate groups.

The invention thus relates to the polymer compositions described herein and the process for their preparation.

The polymer compositions according to the invention are advantageously suitable for stabilizing active substances and effect substances which are sparingly soluble or even insoluble in water in an aqueous phase and therefore permit the preparation of aqueous formulations of such active substances and effect substances, and the preparation of nonaqueous formulations which when diluting with water to an extremely fine distribution of the drug or Effektstoffs lead in the aqueous phase. In contrast to the block copolymers described in the prior art, it is possible to use them to stably solubilize large amounts of active ingredient, based on the polymer, in the aqueous phase.

The present invention therefore also relates to the use of the polymer compositions described here and below for stabilizing active substances and / or effect substances which are poorly or not soluble in water in an aqueous medium. The present invention further relates to the use of the polymer compositions described here for the preparation of formulations of water-insoluble or poorly soluble active ingredients and effect substances. Poor solubility in this context means a solubility of the active substance in water of below 10 g / l, frequently below 5 g / l and especially below 1 g / l and especially below 0.1 g / l at 25 ⁰ C and 1013 mbar.

The invention furthermore relates to active or effect compositions which comprise at least one active substance which is poorly or insoluble in water and / or effect substance and at least one inventive polymer composition, as described here and below.

The active or effect compositions according to the invention can be solid or liquid. A preferred embodiment of such composition relates to an aqueous, i. liquid active ingredient composition comprising an aqueous medium as the continuous phase and at least one disperse phase, wherein the disperse phase at least one active ingredient and / or effect substance, which has a solubility below 10 g / l in water at 25 "C / 1013 mbar, and at least contains a polymer composition according to the invention.

The aqueous active substance compositions of water-insoluble active or effect substances produced using the polymer compositions according to the invention comprise, in addition to an aqueous medium as the continuous phase, at least one active or effect-containing phase in which the active substance and the amphiphilic polymer composition in Form of aggregates of active ingredient or effect material and the polymer constituents of the polymer composition according to the invention are present. This active or effect-containing phase thus forms a disperse phase containing the active substance or the effect substance and at least one inventive polymer composition.

The active substance lies in the continuous aqueous phase in extremely fine to molecularly dissolved form. It is believed that the active ingredient forms aggregates in the aqueous phase with the amphiphilic polymer composition of the present invention. As a rule, these aggregates have average particle sizes below 1 .mu.m, frequently below 500 nm, in particular below 400 nm, especially below 300 nm and especially below 200 nm. Depending on the nature of the polymer and of the active ingredient or effect substance and also on the concentration ratios, the aggregates may also become so small that they are no longer in the form of detectable, discrete particles but in dissolved form (particle size <20 nm or <5 nm). If the aggregates are in the form of discrete particles, the mean is Particle size of the particles often in the range of 5 to 400 nm, preferably in the range of 10 to 300 nm and more preferably in the range of 20 to 200 nm.

A further preferred embodiment of the invention relates to a non-aqueous, generally solid or semi-solid active ingredient composition which has at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C./1013 mbar, and at least one amphiphilic polymer composition containing substantially no or only minor amounts, d. H. Contains <10 wt .-% water. As further constituents, these compositions may contain the typical auxiliaries and additives for the particular application.

The compositions of the invention, i. Both aqueous and nonaqueous compositions, when diluted, give aqueous preparations of the effect substance comprising an aqueous, continuous phase and at least one phase containing active substance having average particle sizes well below 1 μm, typically not more than 500 nm, often not more than 300 nm, in particular not more than 200 nm or 150 nm and especially not more than 100 nm z. In the range of 10 to 300 nm, preferably in the range of 10 to 250 nm, in particular in the range of 20 to 200 nm or 20 to 150 nm and particularly preferably in the range of 30 to 100 nm.

The particle sizes reported herein are weight average particle sizes as determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p. 40ff and literature cited there, and H. Auweter, D. Hom, J. Colloid Interf. Be. 105 (1985) 399, D. Lie, D. Horn, Colloid Polym. Be. 269 (1991) 704 or H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429.

The terms "aqueous medium" and "aqueous phase" here and in the following include water, aqueous mixtures of water with up to 10 wt .-%, based on the mixture, of organic solvents which are miscible with water, and solutions of solids in water or in the aqueous mixtures. Examples of water-miscible solvents include C ₃ -C ₄ ketones such as acetone and methyl ethyl ketone, cyclic ethers such as dioxane and Tetrahydrofuraπ, (VC ^ AIkanole as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert- Butanol, polyols and their mono- and dimethyl ethers such as glycol, propanediol, ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, glycerol, furthermore C ₂ -C ₃ -NiWIe such as acetonitrile and propionitrile, dimethyl sulfoxide, dimethylformamide, formamide, acetamide / d , Dimethylacetamide, butyrolactone, 2-pyrrolidone and N-methylpyrrolidone. The term "functionality" here and below stands for the average number of the respective functional groups R 1 or R 2 per molecule or per polymer chain.

The term active ingredient composition is used here and below synonymously with the term formulation and preparation, i. in the sense of a composition which contains the active substance in concentrated form and which is optionally diluted for use with water or aqueous liquids to the desired concentration of use.

The aqueous active substance compositions according to the invention but also the active substance preparations obtained by diluting an aqueous or non-aqueous active substance composition according to the invention with water are distinguished by extremely high stability against segregation. They can be stored without segregation over a longer period of several months even at elevated temperature and / or at strongly changing temperatures. In addition, more concentrated preparations can be diluted without problems with water, without causing segregation phenomena, such as coagulation, crystallization, flocculation or sedimentation. In addition, the compositions have a high tolerance to electrolytes. In addition, due to the extremely fine distribution, corresponding to the very low apparent particle diameter of the active substance / efficie aggregates, the activity of the active substances or the effect of the effect substances is increased in comparison to conventional formulations. Another advantage is that the active ingredient compositions according to the invention also low in solvents (content of volatile solvents <10 wt .-%, based on the weight of the active ingredient composition) or even solvent-free (content of volatile solvents <1 wt .-%, based on the weight of Active ingredient composition) can be formulated.

A further advantage of the polymer compositions according to the invention is that the active substances can be formulated in solid form. For example, the liquid active substance compositions according to the invention, for example aqueous active substance compositions, but also solutions of the active substance and the polymer composition in an organic solvent, can be dried to form a redispersible solid material, such as, for example, powders or granules. That is to say, by removing the aqueous phase or the organic solvent during drying, finely divided powders or coarse-particle granules are obtained, depending on the drying conditions, which can readily be dissolved or dispersed in water without appreciable enlargement of the teeth occurring. Another advantage of the amphiphilic polymers is the fact that, depending on the configuration of the polymer composition, the solubilizing properties can be controlled via the pH. If, for example, the polymer P1 has carboxyl groups, the solubilizing effect can be reduced by increasing the pH, whereby a spontaneous release of the active ingredient can be achieved. Conversely, basic groups in the polymer can achieve a reduction in solubilization by lowering the pH.

The polymers P1 used for producing the polymer composition according to the invention and also the poly-C ₂ -C ₄ -alkylene ethers P2 have isocyanate-reactive functional groups R 1 and R 2, which react with bond formation with the isocyanate group of the compound V. Examples of suitable functional groups are hydroxyl groups, mercapto groups (SH) and primary and secondary amino groups. Preferred functional groups are hydroxyl groups, in particular hydroxyl groups bound to an aliphatic or cycloaliphatic carbon atom.

Since the isocyanate group-containing compound V has at least 1.5 isocyanate groups per molecule, in the reaction of V with the polymer P1 and the poly-C ₂ -C ₄ -alkyl ether P2, block copolymers form at least partially at least one polymer block, which is derived from the polymer P1, as well as at least one different, hydrophilic polymer block, which is derived from the poly-C ₂ -C ₄ alkylene ether P2, have. In contrast to the amphiphilic block copolymers of the prior art, the blocks are not linked directly to each other, but via a linker having at least two urethane and / or urea groups. In contrast to the block copolymers of the prior art, the polymer compositions obtained generally still to a lesser extent unreacted polymers P1 and / or P2 and symmetrical reaction products, either polymer blocks exclusively derived from polymer P1 or exclusively of poly-C ₂ -C ₄ - alkylene ethers P2 have derived polymer blocks, on. Nevertheless, the advantageous properties of the polymer composition are maintained.

It is assumed that the block copolymers in the polymer compositions according to the invention form aggregates due to the affinity of the functional groups FG present in the polymer blocks P1 for the active substances or effect substances in the aqueous phase with the active compounds. It is further believed that the polymer blocks P1 together with the active ingredients form the core of these aggregates, whereas the hydrophilic polyether chains P2 form the outer regions of the aggregates and thus stabilize the aggregates in the aqueous medium. The affinity of the functional groups FG with the active ingredient to be formulated can be based, for example, on ionic interactions, on nonionic dipole-dipole interactions, on hydrogen bonds, on interactions of π systems or also on mixed forms of these interactions.

Suitable polymers P1 are in principle all polymers composed of ethylenically unsaturated monomers M1 which have the required number of reactive groups R 1 and whose constituent monomers M 1 more than 20% by weight, in particular at least 25% by weight, particularly preferably at least 30 Wt .-% and most preferably at least 35 wt .-% of functionalized monomers M1a include. The proportion of the monomers M1a to the monomers M1 can be up to 100 wt .-% and is advantageously in the range of 25 to 90 wt .-%, in particular in the range of 30 to 80 wt .-%, particularly preferably in the range of 30 bis 70 wt .-% and most preferably in the range of 35 to 60 wt .-%.

In addition to the ethylenically unsaturated double bond, the monomers M1a according to the invention have one or more, for example one or two, functional groups FG. This usually gives the monomers M1a an increased water solubility. The water solubility of monomers M1a, therefore, often is at least 50 g / l and re insbesonde- at least 80 g / l at 25 ⁰ C and 1013 mbar.

The monomers M1a can be acidic or anionic as well as basic or neutral.

In a first preferred embodiment, the monomers M1a essentially comprise only neutral monomers M1a.

In a second preferred embodiment, the monomers M1a essentially comprise only basic monomers M1a.

In a third preferred embodiment, the monomers M1a comprise substantially only acidic monomers M1a

In a fourth preferred embodiment of the invention, the monomers M1a comprise essentially a mixture of neutral and basic monomers M1a. In this embodiment, the weight ratio of neutral to basic monomers is preferably in the range of 1:10 to 10: 1, and more preferably in the range of 5: 1 to 1: 2. In a fifth preferred embodiment of the invention, the monomers M1a essentially comprise a mixture of neutral and acidic monomers M1a. In this embodiment, the weight ratio of neutral to acidic monomers is preferably in the range of 1:10 to 10: 1, and more preferably in the range of 5: 1 to 1: 2.

Among Embodiments 1 to 5, Embodiments 1, 2 and 4 are particularly preferable.

Essentially, here at least 90 wt .-%, and in particular at least 95 wt .-%, based on the weight of the monomers M1a.

Examples of neutral monomers M1a include

- amides and C _r C ₄ -Alkyloxyalkylamide monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, such as acrylamide, methacrylamide, N- (methoxymethyl) (meth) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxyethyl) (meth) acrylamide and the like; monoethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile;

N-vinylamides of aliphatic, cycloaliphatic or aromatic carboxylic acids, in particular N-vinylamides of aliphatic carboxylic acids having 1 to 4 C atoms, such as N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and N-vinylbutyramide; - N-vinyl lactams having 5 to 7 ring atoms, for. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylmorpholinone and N-vinylcaprolactam; monoethylenically unsaturated monomers bearing urea groups such as N-vinyl- and N-allylurea as well as derivatives of imidazolidin-2-one, e.g. N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethyl-imidazolidin-2-one,

N-Allyloxyethylimidazolidin-2-one N- (2-acrylamidoethyl) imidazolidin-2-one, N- (2-acryloxyethyl) imidazolidin-2-one, N- (2-methacrylamidoethyl) imidazolidin-2-one, N- (2 -Methacryloxyethyl) imidazolidin-2-one (= ureidomethacrylate),

N- [2- (acryloxyacetamido) ethyl] imidazolidin-2-one N- [2- (2-acryloxyacetamido) ethyl] imidazolidin-2-one N- [2- (2-methacryloxyacetamido) ethyl] imidazolidin-2-one; Aldehyde- or keto-containing monoethylenically unsaturated monomers such as 3- (acrylamido) -3-methylbutan-2-one (diacetoneacrylamide), 3- (methacrylamido) -3-methylbutan-2-one, 2,4-dioxapentyl acrylate and 2,4-dioxapentyl methacrylate;

Preferred neutral monomers are N-vinyllactams, in particular N-vinylpyrrolidone, and monomers carrying urea groups, in particular N- (2-acrylamidoethyl) imidazolin-2-one and N- (2-methacrylamidoethyl) -imidazolin-2-one.

Examples of basic monomers M1a include

- vinyl-substituted nitrogen heteroaromatics such as 2-, 3- and 4-vinylpyridine, N-vinylimidazole; and monoethylenically unsaturated monomers having a primary, secondary or tertiary amino group, in particular monomers of general formula I.

wherein

X is oxygen or a group NR ^4a ; A is C ₂ -C ₈ alkylene, e.g. B. 1, 2-ethanediyl, 1, 2 or 1, 3-propanediyl,

1,4-butanediyl or 2-methyl-1,2-propanediyl optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms as in 3-oxapentane-1,5-diyl;

R ^1a, R are independently hydrogen, C _r C _Q alkyl, C ₅ -C ₁₀ cycloalkyl, phenyl or phenyl-C _r C ₄ alkyl ^1b and in particular both in each case

C _r C ₄ alkyl;

R ^{2a is} hydrogen or C _r C ₄ alkyl, in particular hydrogen or methyl;

R ^3a is hydrogen or C _r C ₄ -alkyl and in particular hydrogen; and R ^{4a is} hydrogen or C _r C ₄ alkyl and especially hydrogen.

Examples of monomers of the formula I are 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylamide, 3- (N, N-dimethylamino) propyl acrylate , 3- (N, N-dimethylamino) propyl methacrylate, 3- (N, N-dimethylamino) propylacrylamide, 3- (N, N-dimethylamino) propylmethacrylamide and 2- (N, N-dimethylamino) ethylmethacrylamide, wherein (N ₁ N-dimethylamino) propyl methacrylate is particularly preferred. Preferred basic monomers M1a are the monomers of the general formula I.

The monomers M1 a also include anionic or acidic monoethylenically unsaturated monomers. Examples for this are:

monoethylenically unsaturated monomers which have a sulfonic acid group, and the salts of such monomers, in particular the alkali metal salts, for. As the sodium or potassium salts and ammonium salts. These include ethylenically unsaturated sulfonic acids, in particular vinylsulfonic acid, 2-acrylamido

2-methylpropanesulfonic acid, 2-acyl (oxyethanesulfonic acid and 2-methacryloxyethanesulfonic acid, 3-acryloxy- and 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonic acid and its salts, ethylenically unsaturated phosphonic acids such as vinylphosphonic acid and dimethylphosphonylphosphonate and their salts, and monoethylenic unsaturated monomers which carry one or two carboxyl groups, for example α, ß-ethylenically unsaturated C ₃ -C ₈ mono- and C ₄ -C ₈ -D / carboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.

Preferred acidic monomers M1a are the abovementioned monoethylenically unsaturated monomers having one or two carboxy groups.

In addition to the monomers M1a, the polymer may also contain up to <80% by weight of ethylenically unsaturated monomers in copolymerized form, which are different from the monomers M1a. These are preferably neutral, monoethylenically unsaturated monomers M1 b, which have a limited solubility in water of preferably not more than 30 g / l and in particular not more than 20 g / l at 25 ° C and 1 bar. It is suspected that these monomers promote the formation of the drug-polymer aggregates due to hydrophobic interactions. Therefore, the polymers P1 contain, based on the total weight of the monomers M1, preferably up to 10 to 75 wt .-%, in particular to 20 to 70 wt .-%, particularly preferably 30 to 70 wt .-% and especially 40 to 65 wt. -% monomers M1b copolymerized.

The monomers M1b include in particular monomers of the general formula II

wherein

X is oxygen or a group NR ⁴ ; R ^{1 is} C ₁ -C ₂₀ alkyl, C ₅ -C ₁₀ cycloalkyl, phenyl, phenylC _r C ₄ alkyl or phenoxyC _r C ₄ alkyl;

R ^{2 is} hydrogen or C 1 -C ₄ alkyl;

R ^{3 is} hydrogen or C 1 -C ₄ alkyl; and

R _{4 is} hydrogen or C ₁ -C ₄ -AlkVi means.

Preferred monomers of the general formula II are those in which R ³ in formula II represents

Hydrogen stands. In formula II, R ^{2 is} preferably hydrogen or methyl. X in formula II is preferably O, NH, NCH ₃ or NC ₂ H ₅ . and especially preferred for O.

R ¹ in formula II is preferably for

C _r C ₂ o-alkyl, in particular Ci-Cio-alkyl such as ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, 1-pentyl, 2-pentyl, neopentyl, n-hexyl, 2-hexyl, n-octyl, 2-ethyl, 2-propylheptyl, n-decyl, lauryl or stearyl),

C ₅ -C ₀ cycloalkyl such as cyclopentyl, cyclohexyl or methylcyclohexyl,

Phenyl-C _r C ₄ -alkyl, such as benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyl or

Phenoxy-C ₂ -C ₄ alky! such as 2-phenoxyethyl.

In particular, R ¹ is ₀ alkyl C ₂ -C. Also preferably, R ^{1 is} methyl or 2-phenoxyethyl.

Particularly preferred monomers of the formula II are the esters of acrylic acid with C ₂ -C ₁₀ -alkanols (= C ₂ -C ₁₀ -alkyl acrylates), such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2- Ethylhexyl acrylate and 3-propylheptyl acrylate, the esters of methacrylic acid with CrC ₁₀ -alkanols such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and n-hexyl methacrylate. Preferred monomers M1b are also esters of acrylic acid and methacrylic acid with 2-phenoxyethanol such as 2-phenoxyethyl acrylate. Preferred monomers M1b are also the N- (C ₂ -Cio-alkyl) amides of acrylic acid and methacrylic acid and N- (Ci-C ₂ alkyl) -N- (C ₂ -C ₁₀ -alkyl) amides of acrylic acid and the methacrylic acid, z. N-ethylacrylamide, N, N-diethylacrylamide, N-butylacrylamide, N-methyl-N-propylacrylamide, N- (n-hexyl) acrylamide, N- (n-octylacrylamide) and the corresponding methacrylamides. In particular, the monomers M1 b comprise at least 50% by weight, in particular at least 70% by weight, based on the total amount of monomers M1a of at least one C _r C ₄ -alkyl methacrylate (R ¹ = C _r C ₄ -alkyl, R ² = CH ₃ and R ³ = H ), and of these particularly preferably methyl methacrylate and tert-butyl methacrylate.

The monomers M1b also count

vinylaromatic monomers such as styrene, α-methylstyrene, vinyltoluene, etc., olefins having 2 to 20 C atoms, preferably α-olefins having 3 to 10 C atoms such as propene, 1-butene, 1-pentene, 1-hexene, 1 Octenes, diisobutene and 1-decene,

Vinylester of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl nonanoate, vinyl decanoate, vinyl laurate and vinyl stearate, halogenated olefins such as vinyl chloride, C _ir C ₂₀ -alkyl esters of monoethylenically unsaturated monocarboxylic acids with pre preferably 3 to 6 C-atoms, z. B. C _ir C ₂ o-alkyl acrylates and C ₁₁ -C ₂ O-

Alkyl methacrylates, such as lauryl acrylate, lauryl methacrylate, isotridecyl acrylate, isotridecyl methacrylate, stearyl acrylate, stearyl methacrylate,

Di-CrCao-alkyl esters of ethylenically unsaturated dicarboxylic acids having preferably 4 to 8 C atoms, for. B. di-CrCao-alkyl esters of fumaric acid and of maleic acid such as dimethyl fumarate, dirnethyl maleate, dibutyl fumarate and dibutyl maleate,

Glycidyl esters of monoethylenically unsaturated monocarboxylic acids having preferably 3 to 6 carbon atoms, such as glycidyl acrylate and Glyc \ dyimethacry \ at.

Preferred monomers M1 b are the monomers of the general formula II and furthermore vinylaromatic monomers and, among these, in particular styrene. Preferred monomers M1b are also mixtures of the abovementioned monomers M1b which predominantly, in particular at least 60 wt .-% and particularly preferably 70 wt .-%, z. B. 60 to 99 wt .-% or 70 to 99 wt .-%, based on the total amount of the monomers M1b, monomers of the general formula II or a mixture of monomers II with styrene and at least one of them different monomer M1b include.

In addition to the monomers M1a and M1b, the polymers P1 can have up to 20% by weight, in particular not more than 10% by weight, based on the total amount of the monomers M1, of ethylenically unsaturated monomers M1c which are different from the monomers M1a and M1b Included in the package.

The monomers M1c include monoethylenically unsaturated monomers Mick which have at least one cationic group. The monomers Mick include, in particular, those which have a quaternary ammonium group or a quaternized imino group. Examples of monomers having a quaternized imino group are N-alkylvinylpyridinium salts and N-alkyl-N'-vinylimidazolinium salts such as N-methyl-N'-vinylimidazolinium chloride or metosulphate. Among the monomers M1 ck in particular the monomers of general formula IiI are preferred

wherein

R ^{5 is} hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen or methyl,

R ⁶ , R ⁷ and R ⁸ independently of one another are C 1 -C ₄ -alkyl, in particular methyl, and

Y is oxygen, NH or NR ⁹ with R ⁹ = C _r C ₄ -alkyl,

A is C ₂ -C ₃ alkylene, e.g. B. 1, 2-ethanediyl, 1, 2- or 1, 3-propanediyl, 1, 4-butanediyl or 2-methyl-1,2-propanediyl, which is optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms, such as in 3-oxapentane-1, 5-diyl, and

Z ^"stands for an anion equivalent, eg for CP, HSO ₄ ^" , V ₂ SO ₄ ^{2 "} or CH ₃ OSO ₃ ^", etc.

Examples of such monomers are Mick

2- (N, N, N-trimethyl ammonium) ethyl acrylate chloride, 2- (N, N, N-trimethyl ammonium) ethyl methacrylate chloride,

2- (N, N, N-trimethyl ammonium) ethyl methacrylamide chloride,

3- (N, N, N-trimethylammonium) propyl chloride,

S-CN.N.N-Trimethylammoniumjpropylmethacrylat chloride,

3- (N, N, N-trimethylammonium) propylacrylamide chloride, 3- (N, N, N-trimethylammonium) propylmethacrylamide chloride,

2- (N, N, N-trimethylammonium) ethylacrylamide chloride, and the corresponding Me sulfates and sulfates.

The proportion of the monomers Mick in the monomers M1 is advantageously not more than 20% by weight, for example 0.1 to 20% by weight, in particular 0.5 to 15% by weight, and especially 1 to 10% by weight. %. In a preferred embodiment, the polymer P1 contains no or not more than 0.1% by weight of monomers Mick in copolymerized form. The monomers M1c also include monomers M1c.v which have two or more non-conjugated ethylenically unsaturated double bonds. The proportion of such monomers M1c.v will generally be not more than 2% by weight and in particular not more than 0.5% by weight, based on the total monomer amount M1. Examples of these are vinyl and allyl esters of monoethylenically unsaturated carboxylic acids, such as allyl acrylate and allyl methacrylate, di- and polyacrylates of diols or polyols, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butadiene diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol trimethacrylate, tris (hydroxymethyl) ethane triacrylate and trimethacrylate, pentaerythritol triacryiate and trimethacrylate, and also the allyl and methallyl esters of polyfunctional carboxylic acids, such as diallyl maleate, diallyl fumarate, diallyl phthalate. Typical monomers M1c, 3 are also compounds such as divinylbenzene, divinylamine, diallylurea, triallylcyanurate , N, N'-divinyl and N, N'-diallylimidazolidin-2-one, as well as methylene bisacrylamide and methylenebismethacrylamide.

In a particularly preferred embodiment 2a, the polymer contains P1, based on the total amount of monomers M1,

From 20 to 80% by weight, in particular from 25 to 30% by weight, of basic monomers M1a, and from 20 to 80% by weight, in particular from 40 to 75% by weight, of monomers M1b are copolymerized.

In the embodiment 2a, preferred monomers M1a are vinyl-substituted nitrogen heteroaromatics, especially the abovementioned vinylpyridines and the monomers of the formula I. Particularly preferred monomers M1a are the monomers of the formula I.

In the embodiment 2a, preferred monomers M1b are the monomers of the general formula II and furthermore vinylaromatic monomers and, among these, in particular styrene. Preferred monomers M1b are also mixtures of the abovementioned monomers M1b, which are predominantly, in particular at least 60% by weight and more preferably 70% by weight, for. B. 60 to 99 wt .-% or 70 to 99 wt .-%, based on the total amount of the monomers M1b, monomers of the general formula II or a mixture of the monomers II with styrene and at least one of them different monomer M1b include. In particular, the monomers M1b comprise exclusively or almost exclusively (> 95% by weight) monomers of the general formula II and especially a mixture of two or more different esters of acrylic acid or of methacrylic acid (R ² = H or methyl, R ³ = H and X = O).

In a preferred embodiment, the monomers M1b are a mixture of a CrCcAlkylmethacrylat such as methyl methacrylate with a phenyl C 1 -C ₄ -alkyl (meth) acrylate or phenoxy-C 1 -C ₄ -alkyl (meth) acrylate, for example with 2-phenoxyethyl methacrylate.

In a further particularly preferred embodiment 3a, the polymer P1 contains, based on the total amount of the monomers M1,

20 to 80 wt .-%, in particular 25 to 60 wt .-% carboxyl-carrying monomers M1a, and 20 to 80 wt .-%, in particular 40 to 75 wt .-% of monomers M1b polymerized.

In embodiment 3a, preferred monomers M1a are monoethylenically unsaturated mono- and dicarboxylic acids, especially acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid.

In the embodiment 3a preferred monomers M1 b are monomers of the general formula II, C ₂ -C ₁₀ -olefins and Vinyiaromaten particular styrene, C ₁ -C ₈ - alkyl methacrylates such as methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate and 2-ethylhexyl.

According to the invention, the polymers P1 carry reactive functional groups R 1 which react with the isocyanate groups to form bonds. The average number of such groups per polymer molecule (functionality) is usually not more than 3, often not more than 2 and is for example in the range of 0.3 to 3, often in the range of 0.5 to 2, or preferably in the range from 0.3 to 1.8, in particular in the range of 0.5 to 1.5, and especially in the range of 0.6 to 1.4. The functional group R 1 can be arranged in the polymer chain and is preferably located at the end of the polymer chain.

With regard to the use of the polymer composition according to the invention for the formulation of active compounds, the hydrophobic polymer P1 preferably has a number-average molecular weight in the range from 500 to 20,000 daltons and in particular in the range from 1500 to 15,000 daltons.

Polymers P1 are known in principle from the prior art, for example from US 5,556,918 and EP-A 742 238. They are generally prepared by free-radically initiated solution polymerization of the monomers M1 in the presence of an initiator and optionally a regulator, with the proviso that the Initiator at disintegration

Hydroxyl radical (OH radical) or a fragment which has an OH group generated and / or the regulator contains an OH group or an NH ₂ group. SITUATE designated initiators are organic hydroperoxides, such as tert-butyl hydroperoxide, tetrahydro- furanhydroperoxid, cumene hydroperoxide or OH-group-carrying azo initiators such as ^2,2> azobis (2-methyl-N- (2-hydroxyethyl!) propionamide). Suitable regulators are amino alcohols, aminomercaptans, aminophenols and in particular thioalkanols such as 3-hydroxypropanethiol, 2-hydroxyethyl-3-mercaptopropionic acid ester and especially 2-hydroxyethanethiol (mercaptoethanol) and mercaptoglycerol, but also aminomercaptans such as cysteamine (= 2-aminoethanethiol). If such a regulator is used, the polymerization can also be carried out in the presence of a conventional initiator, for example a conventional azo initiator or an organic peroxide such as azobis (isobutyronitrile), di (tert-butyl) peroxide, didecanoyl peroxide, Dibenzoyl peroxide, peracetic acid tert-butyl ester or 2-methylperpropionic acid tert-butyl ester. If the polymerization is carried out in the presence of one of the abovementioned regulators, the regulator is generally added in an amount of from 0.1 to 5% by weight, frequently from 0.2 to 4% by weight and in particular from 0.5 to 3 % By weight, based on the total amount of monomers M1. Initiators are usually added in an amount of 0.05 to 5 wt .-%, often 0.1 to 4 wt .-% and particularly preferably in an amount of 0.2 to 3 wt .-%, based on the polymerizing monomers M1 used.

Examples of suitable solvents for the polymerization of the monomers M1 are alkanols such as methanol, ethanol, n- and isopropanol, aliphatic ketones such as acetone, methyl ethyl ketone, cyclohexanone, alkyl esters of aliphatic carboxylic acids such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-butyl acetate, alicyclic and cyclic ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, aromatic, aliphatic and alicyclic hydrocarbons such as toluene, xylene, hexane, cyclohexane, nitriles such as acetonitrile and N-alkyl actamines such as N-methylpyrrolidone, N - Ethylpyrrolidone and mixtures of these solvents.

For further details, reference is made in particular to page 3 of EP 742 238, to the disclosure of which reference is made.

According to the invention, the polymers P2 are linear or branched poly-C ₂ -C ₄ -alkylene ethers, ie polymers which are essentially, ie at least 90% by weight, based on the weight of the polymers P2 of repeating units of the formula IV

fA-O} (IV)

wherein A is a C ₂ -C ₄ -alkylene group such as ethane-1,2-diyl, propane-1,2-diyl, propane-1, 3-diyl, butane-1, 2-diyl or butane-1 , 3-diyl stands. Among the polymers P2 preference is given to those which are composed of at least 50% by weight, advantageously at least 70% by weight, in particular at least 80% by weight and especially at least 90% by weight, of ethylene oxide unit, ie of groups of formula IV wherein A is 1, 2-ethanediyl. In addition, the aliphatic polyethers may have structural units derived from C ₃ -C ₄ -alkylene oxides.

Among the polymers P2, preference is given in particular to those which have a functionality F2 in the range from 0.5 to 3 and in particular in the range from 0.6 to 2.5 with respect to the functional groups R 2.

The number-average molecular weight of the polymers P2, determined by GPC by customary methods, is preferably in the range from 500 to 20,000 daltons and in particular in the range from 800 to 15,000 daltons.

Particularly preferred polyethers P2 are those of the general formula V

R ^a -X- (CHR ^b -CH _r O) _p -H (V)

wherein

R ^{a is} hydrogen, C _{r is} C ₂ o-alkyl or benzyl, X is oxygen or NH,

R ^{b is} hydrogen or methyl, where at least 50 mol%, in particular at least 70 mol% and preferably at least 90 mol% of the groups R ^{b are} hydrogen, p is an integer whose mean value is in the range from 10 to 500, preferably 20 to 250 and especially 25 to 100 (number average).

Suitable polyethers P2 are known to the person skilled in the art and for the most part are commercially available, for example under the trade names Pluriol® and Pluronic® (polyethers from BASF Aktiengesellschaft).

The total content of the polymers P1 on the polymer composition according to the invention, d. H. the total amount of reacted and unreacted polymer P1 is preferably 9 to 90 and especially 20 to 68 wt .-% of the total weight of polymer P1, polyether P2 and compound V.

The total amount of polyethers P2 on the polymer composition according to the invention, ie the total amount of reacted and unreacted polyether P2, is preferably 9 to 90 and in particular 30 to 78 wt .-% of the total weight of polymer P1, polyether P2 and compound V.

The total amount of compound V on the polymer composition according to the invention, d. H. the total amount of compound V used is preferably from 1 to 20 and in particular from 2 to 15% by weight of the total weight of polymer P1, polyether P2 and compound V.

The weight ratio of polymer P1 to polyether P2 in the novel polymer composition, calculated in each case as the total amount of the polymers used for the preparation, is preferably in the range from 1:10 to 10: 1 and in particular in the range from 1: 4 to 2.2: 1.

Suitable compounds V having a functionality with regard to the isocyanate groups of at least 1.5, in particular 1.5 to 4.5 and especially 1.8 to 3.5 include aliphatic, cycloaliphatic and aromatic di- and polyisocyanates and the isocyanurate, Allophanates, urethdiones and biurets of aliphatic, cycloaliphatic and aromatic diisocyanates.

Preferably, the compounds V have on average from 1.8 to 3.5 isocyanate groups per molecule. Examples of suitable compounds V are aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanates, commercially available mixtures of toluene-2,4- and 2,6-diisocyanate (TDI), n-phenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, cumene 2,4-diisocyanate, 1, 5-naphthalene diisocyanate, p-xylylene diisocyanate, p-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro, 3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4-dimethlyene 1, 3-phenylenediisocyanate, 5,6-dimethyl, 3-phenylenediisocyanate, 2,4-diisocyanatodiphenyl ether, aliphatic diisocyanates such as ethylenediisocyanate, ethylidene diisocyanate, propylene-1,2-diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1 , 10-decamethylene diisocyanate and cycloaliphatic diisocyanates, such as isophorone diisocyanate (IPDI), cyclohexylene-1,2-diisocyanate, cyclohexyl-1, 4-diisocyanate and Bis (4,4'-isocyanatocyclohexyl) methane. Preferred among the diisocyanates are those whose isocyanate groups differ in their reactivity, such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, mixtures thereof and cis and trans isophorone diisocyanate.

In another preferred embodiment of the invention, a biuret or an isocyanurate is used for the preparation of the polymer composition according to the invention. rat of an aliphatic or cycloaliphatic diisocyanate compound, for example, the cyanurate of tetramethylene diisocyanate or of hexamethylene diisocyanate.

To prepare the polymer composition according to the invention, the hydrophobic polymer P1 and the hydrophilic polyether P2 are reacted successively or simultaneously under reaction conditions with the compound V, under which the groups R1 and R2 react with the isocyanate groups to form bonds.

The reaction may be carried out in the absence or in the presence of small amounts thereof, more preferably catalysts which promote the formation of urethanes or ureas. Suitable catalysts are, for example, tertiary amines, for. As triethylamine, tri-n-propylamine, N-methylpyrrolidine, N-methylpiperidine and diazabicyclooctane (DABCO), organotin compounds, especially dialkyltin (IV) salts of aliphatic carboxylic acids such as dibutyltin dilaurate and Dibutylzinndioctoat, 2inn (II) dialkanoate such as tin dioctoate, Tetraalkylorthotitanate as Tetrabutylorthotitanate, as well as cesium salts such as cesium acetate. If desired, the catalyst is added in an amount of not more than 0.1% by weight, based on the compound V, e.g. B. in an amount of 0.01 to 0.1 wt .-%, in particular up to 0.05 wt .-% use.

The required reaction temperatures are naturally dependent on the reactivity of the functional group R 1 or R 2 and the isocyanate compound V and, if used, on the type and amount of catalyst used. It is usually in the range of 10 to 120 ⁰ C and in particular in the range of 15 to 85 ⁰ C.

It goes without saying that the reaction of the polymers P1 and P2 with the isocyanate compound V takes place in the absence of moisture (water content preferably <10000 ppm and in particular <2000 ppm).

The reaction of P1 and P2 with the compound V can be carried out in bulk or in an organic solvent which is inert to the isocyanate groups of the compound V. Examples of suitable solvents are aliphatic ketones such as acetone, methyl ethyl ketone, cyclohexanone, alkyl esters of aliphatic carboxylic acids such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-butyl acetate, alicyclic and cyclic ethers such as diethyl ether, diisopropyl ether, methyl tett-butyl ether, tetrahydrofuran, aromatic, aliphatic and alicyclic hydrocarbons such as toluene, xylene, hexane, cyclohexane, nitriles such as acetonitrile and N-alkyl lactams such as N-methylpyrrolidone, N-ethylpyrrolidone and mixtures of these solvents. The reaction of the polymer P1 and the polymer P2 with the compound V can be carried out successively or simultaneously, ie polymer P1 and P2 can be reacted successively or simultaneously with the compound V.

If the polymers P1 and P2 are reacted successively with the compound V, both the polymer P1 with the compound V and then the polyether P2 with the compound V can be reacted first and vice versa.

If the polymers P1 and P2 are reacted successively with the compound V, the reaction is preferably carried out in such a way that after completion of the reaction with the first polymer P1 or P2 at least 10 mol% to 90 mol%, in particular 20 mol% to 80 mol% of the isocyanate groups in V have reacted with the functional groups R ¹ or R ² and 10 to 90 mol%, in particular 20 to 80 mol% of the isocyanate groups present are still present. Subsequently, the reaction is then carried out with the second polymer P1 or P2. Preferably, therefore, the first polymer P1 or P2 is employed in an amount such that the molar ratio of reactive groups R1 or R2 to the number of isocyanate groups per molecule V is in the range from 0.1: 1 to 0.9: 1 and especially in the range from 0.2: 1 to 0.8: 1. Subsequently, the product thus obtained is reacted with the second polymer, it being preferable to use the second polymer P1 or P2 in such an amount that the total amount of reactive groups R1 + R2 corresponds at least to the number of isocyanate groups of compound V. Preferably, the ratio of R1 + R2 to the total amount of isocyanate groups will not exceed a value of 1.2: 1.

If the polymers P1 and P2 are reacted simultaneously with the isocyanate compound V, the polymers P1 and P2 will preferably be used in an amount such that the molar ratio of reactive groups R1 + R2 to the isocyanate groups is at least 1: 1. Preferably, the ratio R1 + R2 to the total amount of isocyanate groups will not exceed a value of 1.2: 1.

The isocyanate compound V can be used as such in the reaction. However, it is also possible to use the isocyanate compound V in a form in which a part of the isocyanate groups is reversibly blocked by a protective group. Compounds which block (cap or protect) isocyanate groups have been widely described in the literature (see, for example, BZW Wicks, Prague, Org. Coat 3 (1975) 73-99 and 9 (1981) 3-28 or Houben-Weyl , Methods of Organic Chemistry Bd. XIV / 2, p. 61 ff., Georg Thieme Verlag, Stuttgart 1963). Examples of blocking agents of isocyanate groups include phenols, caprolactam, imidazoles, pyrazoles, pyrazolinones, 1,2,4-triazoles, diketopiperazines, malonic esters and oximes. To achieve the success of the invention, however, the use of partially reversibly blocked isocyanates is not required.

In a particularly preferred embodiment of the invention, in a first reaction step, the hydrophobic polymer P1 is prepared by free-radical solvent polymerization in the manner described above and carries out the reaction with the isocyanate V in the liquid reaction mixture thus obtained, without the polymer Isolate P1 in advance. The reaction mixture obtained is then reacted with the polymer P2, preferably a polyether. Alternatively, the desired amount of polyether P2 can be added to the polymer P1 thus prepared, followed by reaction with compound V.

For the preparation of the aqueous active ingredient formulations, the polymer composition obtained according to the invention can be isolated from the reaction mixture. However, it is also possible to use the reaction mixture as such.

In a preferred embodiment of the invention, the solvent used to prepare the polymer composition is partially or completely replaced by water, thereby obtaining an aqueous dispersion of the polymer composition. This can be effected, for example, by first distilling off the solvent and then dispersing the residue in water or in an aqueous medium. Also, one may add water to the solution of the polymer composition and remove the solvent following or in parallel with the addition of the water.

The preparation of the active ingredient composition according to the invention can be carried out in different ways. The preparation of the active substance or effect substance composition according to the invention typically comprises the preparation or provision of a homogeneous, nonaqueous mixture comprising the polymer composition according to the invention and at least one active substance and / or effect substance.

In a first embodiment of the present invention, the aqueous active ingredient composition is prepared by first preparing a homogeneous, nonaqueous mixture consisting of polymer composition and active ingredient and / or effect substance and then dispersing the resulting mixture in water or in an aqueous medium. To prepare the homogeneous, non-aqueous mixture, the active ingredient will generally be incorporated into a liquid form of the polymer composition, for example a melt or, preferably, a solution in an organic solvent. If you use a solvent is then the solvent as far as possible and preferably completely removed, to obtain a solid solution of the active ingredient in the polymer composition. Suitable solvents for this purpose are in principle those which are able to dissolve both the active ingredient and the polymer, for example aliphatic nitriles such as acetonitrile and propionitrile, N, N-dialkylamides of aliphatic carboxylic acids such as dimethylformamide and dimethylacetamide, N-alkyllactams such as N-methylpyrrolidone aforementioned aliphatic and alicyclic ethers, for example tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, dichloroethane and mixtures of the abovementioned solvents. To prepare the aqueous composition according to the invention, the solid solution of the active substance in the polymer composition thus obtained is then dispersed in an aqueous medium by stirring. The stirring can be carried out at temperatures in the range of the ambient temperature as well as at elevated temperature, for example at a temperature in the range from 10 to 80 ^° C. and in particular in the range from 20 to 50 ^° C.

In a second embodiment of the present invention, the preparation of the aqueous active ingredient composition takes place by incorporation of the active ingredient and / or effect substance in an aqueous solution / dispersion of the polymer composition. This is usually done so that the incorporation is carried out at a temperature which is above the melting temperature of the active or Effektstoffs and preferably at a temperature at which the active or Effektstoffschmelze is low viscosity, ie a viscosity in Range of 1 to 1000 mPa.s (according to DIN 53019-2 at 25 ⁰ C). Preferably, the incorporation is carried out using strong shear forces, for example in an Ultraturrax.

In a third embodiment of the invention, the preparation of the aqueous active substance composition is carried out by a process comprising the following steps a to c:

a) preparation of a solution of active ingredient and / or effect substance and optionally polymer composition in an organic solvent which has a boiling point below that of water and b) mixing the solution of the active ingredient and / or effect substance with water or with an aqueous solution of the amphiphilic copolymer and c) removal of the solvent.

In this case, one can alternatively proceed in such a way that the solution of the active substance contains the polymer composition and this solution is mixed with water, or that the solution of the active substance contains only a part of the polymer composition or no polymer. containing mer composition and mixing this solution with an aqueous solution or dispersion of the polymer composition. The mixing can be carried out in suitable stirred vessels, it being possible to submit both water or the aqueous solution of the polymer composition and for this purpose the solution of the active or Ef- fektstoffs, or alternatively presents the solution of the active or effect substance and this the water or the aqueous solution of the polymer composition gives. Then you remove the organic solvent, for. B. by distillation, optionally adding water.

In a preferred variant of this embodiment, the active substance solution and the water or the aqueous solution of the polymer composition are continuously introduced into a mixing zone and continuously remove the mixture from which the solvent is subsequently removed. The mixing zone can be configured as desired. Basically, all apparatuses are suitable for this, which allow a continuous mixing of liquid streams. Such apparatuses are known, for. B. from Continuous Mixing of Fluids (J.-H. Henzler) in Ulimann's Encyclopaedia 5th ed. On CD-Rom, Wiley-VCH. The mixing zone may be configured as static or dynamic mixers or mixed forms thereof. In particular, jet mixers or comparable mixers with nozzles are also suitable as mixing zones. In a preferred embodiment, the mixing zone is the apparatus described in the "Handbook of Industrial Crystallization" (A. S. Myerson, 1993 Butterworth-Heinemann, page 139, ISBN 0-7506-9155-7) or a comparable apparatus.

The volume ratio of active substance solution to water or aqueous solution of the polymer composition according to the invention can be varied over a wide range and is preferably in the range from 10: 1 to 1:20 and in particular in the range from 5: 1 to 1:10.

Naturally, the solvent should be suitable for dissolving the polymer composition according to the invention and the active ingredient in the desired proportions. Suitable solvents can be determined by those skilled in the art by routine experimentation. Examples of suitable solvents are C ₂ -C ₄ -alkanols such as ethanol, n-propanol, n-butanol, isobutanol, the abovementioned aliphatic and alicyclic ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran , Ketones such as acetone, methyl ethyl ketone, lactones such as gamma-butyrolactone, carbonates such as diethyl carbonate, ethylene carbonate, propylene carbonate, lactams such as pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, caprolactam, amides of aliphatic carboxylic acids such as acetamide, N, N-dimethylacetamide, N, N Dimethylformamide, nitriles such as acetonitrile and propionitrile and the like. In a further embodiment of the present invention, a non-aqueous active ingredient composition is prepared by preparing a homogeneous, non-aqueous mixture of inventive polymer composition and active ingredient and / or effect substance. This composition is usually solid if it contains no liquid ingredients. With regard to the preparation of such compositions, what has been said previously in connection with the first embodiment for the preparation of a homogeneous, non-aqueous mixture consisting of amphiphilic polymer composition and active ingredient and / or effect substance in an analogous manner, but optionally at this point desired additives and auxiliaries be incorporated into the composition in a conventional manner. This variant is particularly suitable for the preparation of non-aqueous solid compositions which are solvent-free, but also for the production of solvent-containing formulations.

In the aqueous active compound compositions according to the invention, it has proved to be advantageous if the weight ratio of active ingredient and / or effect substance to polymer composition is in the range from 1:10 to 3: 1 and in particular in the range from 1: 5 to 2: 1.

The content of active and / or effect substance can be varied over wide ranges. In particular, the polymer compositions permit the preparation of so-called active agent concentrates containing the active ingredient in an amount of at least 5% by weight, e.g. B. in an amount of 5 to 50 wt .-% and in particular in an amount of 5 to 20 wt .-%, based on the total weight of the composition.

Advantageously, the compositions according to the invention, in particular the aqueous active ingredient compositions, can be formulated solvent-free or low-solvent, ie the proportion of volatile constituents in the aqueous active ingredient composition is frequently not more than 10% by weight, in particular not more than 5% by weight and especially not more than 1% by weight, based on the total weight of the composition. Volatiles are having such at normal pressure a boiling point below 200 ⁰ C.

In the aqueous compositions according to the invention a multiplicity of preferred active substances and effect substances can be formulated. In particular, the polymer compositions according to the invention are suitable for formulations of organic active compounds, in particular low molecular weight active compounds having a molecular weight below 500 daltons. A particular embodiment of the invention relates to the formulation of active ingredients for crop protection, ie of herbicides, fungicides, neutrophils. mocicides, acaricides, insecticides and agents that regulate plant growth.

Examples of fungicidal active compounds which can be formulated as the aqueous active substance composition according to the invention include the following organic compounds:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;

Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph;

Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl;

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxine and streptomycin, and validamycin A;

Azoles such as bitertanol, bromuconazole, cyazofamide, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, etridazole, fenbuconazole, fluquiconazole,

Flusilazole, flutriafol, fuberidazole, hexaconazole, hymexazole, imazalil, ipconazole, imibenconazole, metconazole, myclobutanil, penconazole, perfuazorate, propiconazole, prochlorazone, prothioconazole, simeconazole, tebuconazole, tetraconazole, thiabendazole, triadimefon, triadimol, triflumizole, triticonazole and 2-butoxy-6-iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl) -

[1, 2,4] triazole-1-sulfonic acid dimethylamide;

2-Methoxybenzophenones, as described in EP-A 897 904 by the general formula I, for. Eg metrafenone;

Dicarboximides such as iprodione, myclozoline, procymidones, vinclozolin; Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram,

Propineb, polycarbamate, thiram, zirconium, zineb;

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxine, cyazofamide, dazomet, dithianone, ethirimol, dimethirimol, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolanes, mepronii, nuarimol, octhilinone, picobezamide,

Sample azoles, proquinazide, pyrifenox, pyroquilon, quinoxyfen, silthiofam; Thiabendazoles, thifluzamide, thiophanate-methyl, tiadinil, tricyclazoles, triforines, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine, and bupirimate;

Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic isopropyl;

Phenylpyrroles such as fenpiclonil and fludioxonil;

Unclassified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, diclomethine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, Ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalides, Toloclof os-methyl, quintozene, zoxamide, isoprothiolane, fluopicolide (picobenzamide); Carpropamide, mandipropamide, N- (2- {4- [3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl} ethyl) -2-methanesulfonylamino-3-methyl-butyramide,

N- (2- {4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl} -ethyl) -2-ethanesulfonyl-amino-3-methyl-butyramide; Furametpyr, thiflucamide, penthiopyrad, fenhexamid, 3,4-dichloroisothiazole-5-carboonic acid (2-cyano-phenyl) -amide, flubenthiava-carb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino methyl propionate, methyl 2-chloro-5- [1- (6-methylpyridiπ-2-ylmethoxyimino) ethyl] benzyl} carbamate, {2-chloro-5- [1- (3-methylbenzyloxyimino) ethyl] ] - Benzylj-carbamic acid methyl ester, Flusulfamide, amides of the formula

wherein

X for CHF ₂ or CH ₃ ; and

R ¹ , R ^{2 are} independently halogen, methyl or halomethyl, z. CF ₃ ; stand;

Strobilurins as described in WO 03/075663 by the general formula I, for example azoxystrobin, dimoxystrobin,

Fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, and trifloxystrobin;

Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;

Cinnamic acid amides and analogs such as dimethomorph, flumetover, flumorp; 6-Aryl- [1,2,4] triazolo [1,5-a] pyrimidines as described, for example, in US Pat. In WO 98/46608,

WO 9941255 or WO 03/004465 are each described by the general formula I, for. For example, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine;

Amide fungicides such as cyclofenamide and (Z) -N- [σ- (cyclopropylmethoxyimino) -2,3-difluoro-6- (difluoromethoxy) benzyl] -2-phenylacetamide.

Examples of herbicides that can be formulated as the aqueous active ingredient composition of the present invention include:

«1, 3,4-thiadiazoles such as buthidazole and cyprazole; Amides such as allidochlor, benzoylpropyl, bromobutide, chlorthiamide, dimepiperate, dimethenamid, diphenamid, etobenzanide, flampropymethyl, fosamiπ, isoxaben, metazachlor, monalides, naptalame, pronamide, propane;

Aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate, sulfosates;

Aminotriazoles such as amitrole, anilides such as anilofos, mefenacet;

Anilides such as anilofos, mefenacet;

Aryloxyalkanoic acid such as 2,4-D, 2,4-DB, Clomeprop, dichlorprop, dichlorprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napro-panilide, triclopyr;

Benzoic acids such as Chloramben, Dicamba;

Benzothiadiazinones, such as bentazone;

Bleachers such as Clomazone, Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazolate, Sulcotrione; Carbamates such as carbetamide, chlorobufam, chloropropham, desmedipham,

Phenmedipham, Vernolate;

Quinolinic acids such as Quinclorac, Quinmerac;

• dichloropropionic acids such as dalapon;

• dihydrobenzofurans such as ethofumesates; • dihydrofuran-3-one, such as flurtamone;

Dinitroanilines such as Benefin, Butraline, Dinitramine, Ethalfluralin, Fluchloralin, Isopropaline, Nitralin, Oryzalin, Pendimethalin, Prodiamine, Profluralin, Trifluralin,

Dinitrophenols such as bromofenoxime, dinoseb, dinoseb acetate, dinoterb, DNOC, minoterb acetate; Diphenyl ethers such as acifluorfen-sodium, acionifen, bifenox, chlomitrofen,

Difenoxuron, ethoxyfen, fluorodifene, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;

Dipyridyls such as cyperquat, difenzoquat-methylsuifate, diquat, paraquat-dichloride;

Imidazoles such as isocarbamide; Imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazethabenz-methyt,

Imazethapyr, Imazapic, Imazamox;

Oxadiazoles such as methazoles, oxadiargyl, oxadiazon;

• oxiranes like Tridiphane;

Phenols, such as bromoxynil, loxynil; Phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofop-butyl, diclofopmethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl , Isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl; Phenylacetic acids such as chlorfenac;

• phenylpropionic acids such as chlorophenprop-methyl;

Ppi agents such as benzofenap, flumiclorac-pentyl, flumioxazine, flumipropyne, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimin; • pyrazoles such as Nipyraclofen;

Pyridazines such as Chloridazon, Maleic hydrazide, Norflurazon, Pyridate;

Pyridinecarboxylic acids such as clopyralid, dithiopyr, picloram, thiazopyr;

Pyrimidyl ethers such as pyrithia-bac acid, pyrithiobac-sodium, KIH-2023, KIH-6127;

• sulfonamides such as flumetsulam, metosulam; Triazole carboxamides such as triazofenamide;

Uracils such as bromacil, lenacil, terbacil;

• Benazoline, Benfuresate, Bensulide, Benzofluor, Bentazone, Butamifos, Cafenstrole, Chlorthal-dimethyl, Cinmethylin, Dichlobenil, Endothall, Fluoroben- tranil, Mefluidide, Perfluidone, Piperophos, Topramezone and Prohexadione-Calcium;

Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, Rimsul - furon, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron;

• Cyclohexenone-type pesticides such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim. Very particularly preferred cyclohexenone-type herbicidal active compounds are: tepraloxydim (compare AGROW, No. 243, 3.11.95, page 21, caloxydim) and 2- (1- [2- {4-

Chlorophenoxy} propyl-oxyimino] butyl) -3-hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2-cyclohexen-1-one and of the sulfonylurea type: N - (((4-methoxy-6-) trifluoromethyl] -1, 3,5-triazin-2-yl) amino) carbo-nyl) -2- (trifluoromethyl) -benzenesulfonamide.

Examples of insecticides that can be formulated as the aqueous active agent composition of the present invention include:

Organo (thio) phosphates, such as acephates, azamethiphos, azinphos-methyl, chloropyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorophos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoates, disulphoton, ethion, EPN, fenitrothion, fenthion, isoxathion , Malathion, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone, phorate, phoxim, Pirimiphos-methyl, profenofos, prothiofos, primiphos-ethyl, pyraclofos, pyridaphenthione, sulprophos, triazophos, trichlorfon; Tetrachlorvinphos, vami- dothione

Carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran,

Carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates;

Pyrethroids such as Allethrin, Bifenthrin, Cyfluthrin, Cycloprothrin, Cypermethrin, Cyphenothrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin, Imoprothrin, Lambda-Cyhaiothrin, Permethrin, Prallethrin, Pyrethrin I, Pyrethrin II, Silafluofen, Tau-Fluvalinate , Tefiuthrin, traiomethrin, transfluthrin, alpha-cypermethrin, zeta-cypermethrin, permethrin;

• Arthropod growth regulators: a) chitin synthesis inhibitors z. B. benzoylureas such as chlorofiuazuron, cyromacin, diflubenzuron, flucycloxuron, flufenonoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists such as halofenozides, methoxyfenozides, tebufenozides; c) juvenoids such as pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors such as spiroidalofen;

Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiomethoxam, nitenpyram, nithiazine, acetamiprid, thiacloprid;

• Other unclassified insecticides such as abamectin, acequinocyl, acetamiprid, amitraz, azadirachtin, bensultap bifenazate, cartap, chlorfenapyr, chlordime form, cyromazine, diafenthiuron, dinetofuran, diofenolan, emamectin, endosulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochloride , gamma-HCH hydramethylnone, imidacloprid, indoxacarb, isoprocarb, metolcarb,

Pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, pyridalyl, flonicamid, fluacypyrim, milbemectin, spiromesifen, flupyrazofos, NC 512, tolfenpyrad, flubendiamide, bistrifluron, benclothiaz, pyrafluprole, pyriprole, amidoflumet, flufenerim, cyflumetofen, acequinocyl, lepimectin, profluthrin , Dimefluthrin, amidrazone, metaflumizone, N-R'-2,2-dihalo-1-R "- cyclopropanecarboxamide-2- (2,6-dichloro-α, α, σ-trifluoro-p-tolyl) hydrazone, N-R'-2,2-di (R ¹ ") propionamide-2- (2,6-dichloro-a, ü ', ύ'-trifluoro-p-tolyl) hydrazone, halo being chlorine or bromine, R 'is methyl or ethyl, R "is hydrogen or methyl and R " ^{1 is} methyl or ethyl, XMC and xylylcarb xylylcarb and compounds of the following formulas

Aminoisothiazoles of the formula

wherein

R = -CH ₂ O-CH ₃ or H and

R = -CF ₂ CF ₂ CF ₃ ;

Anthranilamide of the formula

wherein R is C _r C ₄ alkyl such as methyl, ethyl, isopropyl or n-butyl, and the compound of the following formula

N-phenylsemicarbazones, as described in EP-A 462456 by the general formula I, in particular compounds of the general formula V

wherein R ¹¹ and R ¹² are independently hydrogen, halogen, CN, C ₁ -C ₄ -alkyl ₁ C ₁ -C ₄ -alkoxy, Ci-C ₄ haloalkyl or C _r C ₄ haloalkoxy and R ¹³ is C ₁ -C ₄ -alkoxy, CrC ₄ haloalkyl or C _r C ₄ haloalkoxy is, for example. B. Compound IV where R ^{11 is} 3-CF ₃ and R ^{12 is} 4-CN and R ^{13 is} 4-OCF ₃

(Metaflumizone).

Useful growth regulators are z. As chormoquat chloride, mepiquat chloride, prohexadione calcium or the group of gibberellins. These include z. B. the gibberellins GA ₁ , GA ₃ , GA ₄ , GA ₅ and GA _7, etc. and the corresponding exo-16,17-Dihydrogibberelline and the derivatives thereof, for. As the esters with CrC ₄ carboxylic acids. Preferred according to the invention is the exo-16,17-dihydro-GA ₅ -13-acetate, furthermore 1-naphthylacetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, 3-CPA, 4-CPA, ancymidol, anthraquinone, BAP ₁ butifos; Tribufos, Butralin, Chlorflurenol, Clofencet, Cyclanilide, Daminozide, Dicamba, Dikegulac sodium, Dimethipine, Chlorfenethol, Etacelasil,

Ethephon, ethychlozate, fenoprop, 2,4,5-TP, fluoride amide, flurprimidol, flutriafol, guazatine, imazalil, indolylbutyric acid, indolylacetic acid, karetazan, kinetin, lactidichloroethyl, maleic hydrazide, mefluidide, naptalam, paclobutrazole, quinmerac, sintofen , Tetcyclacis, Thidiazuron, Triiodobezoicacid, Triapenthenol, Triazethane, Tribufos, Trinexapac-ethyl and Uniconazole.

A preferred embodiment of the invention relates to the use of the polymer compositions according to the invention for the preparation of active ingredient compositions, in particular aqueous active ingredient compositions of fungicides, in particular strobilurins, azoles and 6-aryltriazolo [1, 5a] pyrimidines, as described, for. In WO 98/46608, WO 99/41255 or WO 03/004465 are each described by the general formula I, in particular for active compounds of the general formula VI,

wherein

R ^{x is} a group NR ¹⁴ R ¹⁵ , or linear or branched C ₁ -C ₈ -alkyl which is optionally substituted by halogen, OH, C ₁ -C ₄ -alkoxy, phenyl or C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ -alkenyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkenyl, phenyl or naphthyl, where the 4 last mentioned radicals 1, 2, 3 or 4 substituents selected from halogen, OH, C ₁ -C ₄ -Alk ^ ₁ C _r C ₄ -haloalkoxy, C ₁ -C ₄ -alkoxy and Ci-C ₄ -haloalkyl may have;

R ^14, R ¹⁵ are independently hydrogen, C _r C _s alkyl,

C ^ Ca-haloalkyl, C ₃ -C ₀ cycloalkyl, QrCe halocycloalkyl, C ₂ -C ₈ alkenyl, C ₄ -C ₀ -alkadienyl, C ₂ -C ₈ haloalkenyl, C ₃ -C ₆ -cycloalkyl alkenyl, C ₂ -C ₈ -halocycloalkenyl, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl or C ₃ -C ₆ -cycloalkynyl,

R ¹⁴ and R ¹⁵ together with the nitrogen atom to which they are attached, five- to eight-membered heterocyclyl which is bonded via N and one, two or three further heteroatoms from the group O, N and S as a ring member and / or one or more substituents from the group halogen, C _r C ₆ alkyl, CRCE haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ halo-alkenyl, C ₁ -C ₆ -alkoxy, C _r C ₆ - Haloalkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ halo genoalkenyloxy, (exoJ-CrCe-alkylene and oxy-CrC ₃ -alkylenoxy can carry;

L is selected from halogen, cyano, C _r C ₆ alkyl, CrC ₄ -Halgoenalkyl,

C ₁ -C ₆ alkoxy, C ₁ -C ₄ haloalkoxy and C ₁ -C ₆ alkoxycarbonyl;

L ^{1 is} halogen, CrC ₆ -alkyl or -C ₆ haloalkyl and in particular fluorine or chlorine;

X is halogen, C ₁ -C ₄ -alkyl, cyano, C ₁ -C ₄ -alkoxy or CrC ₄ -haloalkyl, preferably halogen or methyl and in particular chlorine.

Examples of compounds of the formula VI are 5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 - (4-methylpipera2in-1-yl) -6- (2,4,6-trifluorophenylH1,2,4] triazolo [1,5-a] pyrimidine, δ-chloro-T-cmorpholine-i-yO-θ ^ ^ .beta-trifluorophenyl O-ri ^^ triazoloIl. S -pyryridine, 5-chloro-7- (piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4-yliazolo [1, 5-a] pyrimidine, 5-chloro-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl!) - [1, 2,4] triazo! O [1, 5 a] pyrimidine, 5-chloro-7- (isopropylamino) -6- (2 ₎ 4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- ( cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (2,2,2-trifluoroethylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (1,1-t-fluoropropan-2-ylamino) -6- ( 2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7- _(3> 3-dimethyl-butan-2-ylamino) -6- (2 _I 4 _l 6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1,2- _I ] triazolo [1,5-a] pyrimidine, 5-chloro-7- (cyclohexyl) -6 (2 _l 4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (2-methylbutan-3-yl) -6- (2 ₎ 4 ₎ 6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 - (3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (4-methylcyc ! ohexan-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (hexan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (2-methyl-1-butan-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] -tiazolo [1, 5-a] pyrimidine, 5-chloro-7 - (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (1-methylpropane 1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (4-methylpiperidin-1-yl) -6- (2 ₎ 4,6-trifluorophenyl) - [1 _l 2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (4-methylpiperazin-1-yl) -6- _(2,4) 6-trifluorophenyl) - [1, 2,4JWaZoIo [1, 5- a] pyrimidine,

5-Methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- ( piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (morpholin-1-yl) - 6- (2,4,6-trifluorophenylH1, 2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (isopropylamino) -6- (2 ₎ 4,6-trifluorophenyl) - [1 _I 2 _I 4] triazolo [1,5-a3pyrimidine, 5-methyl-7- (cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine , 5-methyl-7- _(2,2) 2-trifluoroethylamino) -6- (2,4 _I 6-trifluorophenyl) - [1, 2 _I 4] triazolo [1,5-a] pyrimidine, 5-methyl- 7- (1,1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenylH1, 2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- _(3> 3-dimethyl-butan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1 _l 5-a] pyrimidine,

5-Methyl-7- (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1 _I 2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclohexyl) -6 - (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (2-methylbutan-3-yl) -6- (2,4 _I 6-trifluorophenyl) - [1, ₂₎ 4] triazolo [1 _l 5-a] pyrimidine, 5-methyl-7 - (3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (4-methylcyclohexane 1 -yl) -6- (2,4,6-trifluorophenyl) ~ [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (hexan-3-yl) -6 - (2,4,6-trifluorophenylH1, 2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (2-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenylH1,2,4] triazolo [1,5-a] pyrimidine and 5-methyl-7- (1-methylpropan-1-yl ) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-ajpyrimidine.

A preferred embodiment of the invention accordingly also relates to the use of the polymer compositions according to the invention for stabilizing or solubilizing fungicides, in particular strobilurins, azoles and 6-aryltriazolo- [1, 5a] pyrimidines, as described, for example, in US Pat. In WO 98/46608, WO 99/41255 or WO 03/004465 are each described by the general formula I, in particular for active compounds of the general formula VI, in the aqueous phase.

A further preferred embodiment of the invention relates to the use of the polymer compositions according to the invention for the preparation of active compound compositions, in particular for preparing aqueous active ingredient compositions of insecticides, in particular arylpyrroles such as chlorfenapyr, of pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, Esfen- valerate, ethofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin and permethrin, of neonicotinoids and of semicarbazones of formula V.

A preferred embodiment of the invention accordingly also relates to the use of the polymer compositions according to the invention for stabilizing or solubilizing insecticides, in particular arylpyrroles, of pyrethroids, of neonicotinoids and of semicarbazones of the general formula V, in the aqueous phase.

In addition, the polymer compositions according to the invention are suitable for the preparation of active ingredient compositions, in particular aqueous active ingredient compositions of pharmaceutical active ingredients and prodrugs. These include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, platelet aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroid therapeutics, psychotropic drugs, Parkin and other anti-hyperkinetics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering agents, hepatic therapies, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport proteins , Enzyme inhibitors, emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics, biliary tract therapeutics, anti-asthmatics, broncholytics, beta-receptor blockers, calcium antagonists, ACE inhibitors, arteriosclerotic agents, antiphlogistics, anticoagulants, antihypotonics, antihypoglycemics, antihypertensives, antifibrinolytics, antiepileptics, Antiemetics, antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergic drugs, anthelmintics, analgesics, analeptics, aldosterone antagonists, weight loss agents. Examples of suitable active pharmaceutical ingredients are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170.

The polymer compositions according to the invention are furthermore suitable for the preparation of preparations, in particular aqueous preparations of cosmetic active ingredients, in particular of cosmetic oils and fats such as peanut oil, jojoba oil, coconut oil, almond oil, olive oil, palm oil, castor oil, soybean oil or wheat germ oil, essential oils such as mountain pine oil, lavender oil, Rosemary oil, pine needle oil, pine needle oil, eucalyptus oil, peppermint oil, sage oil, bergamot oil, turpentine oil, lemon balm oil, sage oil, juniper oil, lemon oil, aniseed oil, cardamom oil; Peppermint oil, camphor oil etc. or for mixtures of these oils.

In addition, the polymer compositions according to the invention are suitable for the preparation of preparations, in particular aqueous preparations of food supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.

Accordingly, the polymer compositions of the invention are also suitable for stabilizing the aforementioned active ingredients in the aqueous phase.

Examples of effect substances which can be formulated as aqueous active substance composition according to the invention are:

Dyes: z. For example, the dyes described in DE-A 102 45 209 and the color Index referred to as a disperse dyes and as solvent dyes compounds, which are also referred to as disperse dyes. A compilation of suitable disperse dyes can be found, for example, in Ullmanns Enzyklopädie der technischen Chemie, 4th Edition, Vol. 10, pp. 155-165 (see also Vol. P. 585ff - anthraquinone dyes; Vol. 8, p. 244ff - azo dyes; Vol. 9, p. 313ff - quinophthalone dyes). This reference and the compounds mentioned therein are hereby incorporated by reference. Disperse dyes and solvent dyes which are suitable according to the invention include a wide variety of different chromophore classes of dyes, for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes. Examples of disperse dyes which are suitable according to the invention are the disperse dyes of the following color index list: CI Disperse Yellow 1 - 228, CI Disperse Orange 1 - 148, CI Disperse Red 1 - 349, CI Disperse Violet 1 - 97, CI Disperse Blue 1 - 349, CI Disperse

Green 1 - 9, C.I. Disperse Brown 1 - 21, C l. Disperse Black 1 - 36. Examples of solvent dyes which are suitable according to the invention are the compounds of the following list of concentrates: CI Solvent Yellow 2 - 191, CI Solvent Orange 1 - 113, CI Solvent Red 1 - 248, CI Solvent Violet 2 - 61, C l. Solvent Blue 2 - 143, C I. Solvent Green 1 - 35, CI Solvent Brown 1 - 63, CI Solvent Black 3 - 50. Dyes which are suitable according to the invention are furthermore derivatives of naphthalene, of anthracene, of perylene, of terylene, of quarterylene, and diketopyrrolopyrrole dyes, perinone dyes, coumarin dyes, isoindoline and isoindolinone dyes, porphyrin dyes, phthalocyanine and naphthalocyanine dyes; and

UV absorbers: in particular compounds from groups a to g below

a) 4,4-diarylbutadienes, b) cinnamic acid esters, c) benzotriazoles, d) hydroxybenzophenones, e) diphenylcyanoacrylates, f) oxamides, g) 2-phenyl-1,3,5-triazines;

The group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula A.

The compounds are known from EP-A-916 335. The substituents _R 1 and / or _R n are preferably C _r C _a -alkyl and C ₅ -C ₈ -cycloalkyl.

The group b) of the cinnamic acid esters includes, for example, 2-isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl α-methoxycarbonyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α- cyano-.beta.-methyl-p-methoxy-cinnamate and methyl-.alpha.-methoxycarbonyl-p-methoxycinnamate.

The group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5 ¹ -methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl) 2 ¹ -hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1, 1, 3,3-tetramethylbutyl) phenyl) benzotriazole , 2- (3 ¹ , 5'-di-tert-butyl-2 ¹ -hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 ¹ -methylphenyl) -5 - chloro-benzotriazole, 2- (3 ^I -sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole,

2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) - benzotriazole, 2- (3 ^I, 5'-bis- (α, α-dimethylbenzyl) -2 ^I -hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 ^I - [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy- 5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 ¹ -tert-butyl-2 ¹ -hydroxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3 ' -tert-butyl-2-hydroxy-5 ^I ^I - (2-octyloxycarbonylethyl) phenyl) - benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2' hydroxyphenyl) - benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5 ^{I-methylphenyl)} benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) - phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; the product of the esterification of 2- [3'-tert-butyl -5 ^I - (2-methoxycarbonylethyl) -2 '-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) 3] 2. with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl and mixtures thereof.

Examples of groups d) of hydroxybenzophenones include 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzo-phenone , 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ¹ -dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy-4- (n-octyl oxy) benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 2.2 ¹ - Dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bisulfonic acid and its sodium salt. The group e) of the diphenylcyanoacrylates includes, for example, ethyl 2-cyano-3,3-diphenyl acrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate, which is commercially available, for example, as Uvinul® 3039 from BASF AG, Ludwigshafen, and 1.S-bis-KZ-cyano-S'.S'-diphenylacryloyOoxyl-a ^ -bisIP'-cyano-S '.S'-diphenyl-acryloyl) oxy] methyl} propane, which is commercially available, for example, under the name Uvinul® 3030 from BASF AG, Ludwigshafen.

The group f) of the oxamides includes, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5 , 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-Ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides.

Group g) of 2-phenyl-1,3,5-triazines includes, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4 , 6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3.5 triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) -phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy) tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3 -dodecyloxypropoxy) phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-tri azine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3-yne, 5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

In addition to the abovementioned constituents, the aqueous active substance compositions according to the invention may also contain conventional surface-active substances and other additives. Surfactants include surfactants, dispersing aids and wetting agents. The other additives include in particular thickeners, defoamers, preservatives, antifreeze stabilizers, etc. In principle, anionic, cationic, nonionic and amphoteric surfactants are usable, with polymer surfactants and surfactants with heteroatoms being included in the hydrophobic group.

The anionic surfactants include, for example, carboxylates, especially alkali, Erdaikali- and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g. For example, sodium lauroyl sarcosinate; taurates; Methylcelluloses; Alkyl phosphates, especially mono- and diphosphoric acid alkyl esters; Sulfates, in particular alkyl sulfates and alkyl ether sulfates; Sulfonates, other alkyl and alkylarylsulfonates, in particular alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids and aikylsubstituierten arylsulfonic, alkylbenzenesulfonsäuren such as lignin and phenolsulfonic, naphthalene and Dibutylnaphthalinsυlfonsäuren, or Dodecylbenzofsulfonate, Afkyfnaphthalinsul-, Fonate, Alkylmethylestersulfonate, condensation products of sulfonated Naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalenesulfonic acids, phenol- and / or phenolsulfonic acids with formaldehyde or with formaldehyde and urea, mono- or dialkylsuccinic acid sulfonates; as well as protein hydrolysates and lignin sulphite waste liquors. The aforementioned sulfonic acids are advantageously used in the form of their neutral or optionally basic salts.

The cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and also pyridine and imidazoline derivatives, in particular alkylpyridinium halides.

Nonionic surfactants include, for example:

Fatty alcohol polyoxyethylene esters, for example, lauryl alcohol polyoxyethylene ether acetate, alkyl polyoxyethylene and polyoxypropylene ethers, e.g. From iso-tridecyl alcohol and fatty alcohol polyoxyethylene ether,

Alkylaryl alcohol polyoxyethylene ethers, e.g. Octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates, glycerol esters such as glyceryl monostearate,

Fatty alcohol alkoxylates and oxo alcohol alkoxylates, in particular of the RO- (R ₁₈ O) _r (R ₁₉ O) _s R ₂ O type, with R ₁₈ and R ₁₉ independently of one another = C ₂ H ₄ , C ₃ H ₈ , C ₄ H ₈ and R ₂₀ = H, or C ₁ -C ₁₂ -alkyl, R = C ₃ -C ₃₀ alkyl or C 6 -C ₃₀ -alkenyl, r and s is 0 to 50, where not both be 0 independently of one another, such as iso-tridecyl alcohol and oleyl alcohol polyoxyethylene ethers, Alkylphenolalkoxylate, such as ethoxylated iso-octyl, octyl or nyl-phenol, tributylphenol polyoxyethyl ether,

Fatty amine alkoxylates, fatty acid diethanolamide and fatty acid diethanol amide alkoxylates, in particular their ethoxylates, sugar surfactants, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides, alkylmethyl sulfoxides,

Alkyldimethyiphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.

The amphoteric surfactants include, for example, sujfobetaines, carboxybetaines and alkyldimethylamine oxides, e.g. B. tetradecyldimethylamine oxide.

Other surfactants which are to be mentioned as examples here are perfluorurfactants, silicone surfactants, phospholipids, such as, for example, lecithin or chemically modified lecithins, amino acid surfactants, eg. B. N-Lauroy) glutamate.

Unless specified, the alkyl chains of the surfactants listed above are linear or branched radicals having usually 8 to 20 carbon atoms.

(n execution of a ^'form not contain aqueous active compound composition according to the invention more than 10 wt .-%, preferably not more than 5 wt .-% and especially not more than 3 wt .-%, eg. 0.01 to 5 wt % or 0.1 to 3% by weight of conventional surface-active substances, in each case based on the total amount of active ingredient and polymer composition The conventional surface-active substances then preferably make no more than 5% by weight and in particular not more than 3% by weight %, for example 0.01 to 5 wt .-% or 0.1 to 3 wt .-%, based on the total weight of the composition of.

Depending on the application, however, it may be advantageous if the active substance compositions according to the invention are formulated with surface-active substances. Then, the proportion of conventional surface-active substance is often in the range of 0.5 to 30 wt .-%, in particular in the range of 1 to 20 wt .-%, based on the total amount of active ingredient and polymer composition, or in the range of 0, From 2 to 20% by weight and in particular from 0.5 to 15% by weight, based on the total weight of the formulated composition.

Although an advantage of the compositions according to the invention is their low content of volatile organic substances, it can be used for some applications. desires to be the compositions of the invention with organic solvents, oils and fats, preferably such solvents or oils and fats that are environmentally friendly or biocompatible, such as the aforementioned water-miscible solvents or solvents, oils or fats with water or only very limited miscible are to formulate, for. B. with one or more of the following substances:

Paraffin oils, aromatic hydrocarbons and aromatic hydrocarbon mixtures, e.g. B xylene, Solvesso 100, 150 or 200, and the like, phenols and alkylphenols, e.g. Phenol, hydroquinone, nonylphenol, etc.

Ketones with more than 4 carbon atoms, such as cyclohexanone, isophorone, isopherone, acetophenone, acetonaphthone,

Alcohols with more than 4 carbon atoms, such as acetylated lanolin alcohol, cetyl alcohol, 1-decanol, 1-heptanol, 1-hexanol, isooctadecanol, isopropyl alcohol, oleyl alcohol, benzyl alcohol,

Carboxylic esters, e.g. Dialkyl adipates such as adipic acid bis (2-ethylhexyl) ester, dialkyl phthalates such as 2-ethylhexyl phthalate, alkyl acetates (also branched alkyl groups) such as ethyl acetate and acetoacetate, stearates such as butyl stearate, glycerol monostearate, citrates such as acetyltributyl citrate, furthermore cetyl octanoate, methyl oleate, methyl p-hydroxybenzoate, methyltetradecanoate, propyl-p-hydroxybenzoate, methylbenzoate, lactic acid esters such as isopropyl lactate, butyl lactate and 2-ethylhexyl lactate, vegetable oils such as palm oil, rapeseed oil, castor oil and derivatives thereof such as oxygenated, coconut oil, cod liver oil, corn germ, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame seed oil, grapefruit oil, basil oil, apricot oil,

Ginger oil, geranium oil, orange oil, rosemary oil, macadamia oil, onion oil, mandarin oil, pine oil, sunflower oil, hydrogenated vegetable oils such as hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated soybean oil, - animal oils such as lard oil, fish oils,

Dialkylamides medium to long-chain fatty acids z. B. Hallcomide and vegetable oil esters such as rapeseed oil methyl ester.

Suitable thickeners are compounds which give the formulation a pseudoplastic flow behavior, ie high viscosity at rest and low viscosity in the agitated state. Here, for example, polysaccharides or organic layer minerals such as Xanthan Gum ^® (Kelzan ^® from. Kelco), Rhodopol ^® 23 (Rhone Poulenc) or Veegum ^® (from RT Vanderbilt) or Attaclay ^® (Engelhardt) to call, said xanthan gum ^{® is} preferably used. As suitable for the dispersions according to the invention anti-foaming agents, for example, silicone emulsions (such. As silicone ^® SRE, from Wacker, or Rhodorsil ^® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.

Bactericides may be added to stabilize the compositions of the invention against attack by microorganisms. Suitable bactericides are, for example Proxel ^® from. ICI or Acetide ^® RS from. Thor Chemie and Kathon ^® MK from Rohm & Haas.

Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are usually used in amounts of not more than 10% by weight, based on the total weight of the active ingredient composition, in order not to exceed the desired content of volatile compounds. In one embodiment of the invention, the proportion thereof of various volatile organic compounds is preferably not more than 1 wt .-%, in particular not more than 1000 ppm.

If appropriate, the aqueous active ingredient compositions according to the invention may contain from 1 to 5% by weight of buffer, based on the total amount of the formulation prepared for pH regulation, the amount and type of buffer used being governed by the chemical properties of the active ingredient (s) , Examples of buffers are alkali salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.

The invention further solid active ingredient composition comprising at least one amphiphilic polymer composition as described herein and at least one finely divided in the polymer composition active ingredient and / or Ef- fektstoff which has a solubility in water at 25 ° C / 1013 mbar below 10 g / l and which is typically selected from the aforementioned active ingredients. The solid active substance compositions according to the invention can be dispersed in water and then give the aqueous active substance compositions according to the invention. Surprisingly, the aqueous active substance compositions obtained in this way are also characterized by very fine distribution of the active ingredients in the continuous aqueous phase, the particle sizes given above being obtained and substantially not exceeded. The solid drug compositions typically contain the drug and / or effect substance and the amphiphilic polymer composition in a weight ratio of 1:10 to 3: 1, and more preferably in the range of 1: 5 to 2: 1.

The solid active substance composition according to the invention can be obtained, for example, by drying an aqueous active compound composition according to the invention, by dissolving the active ingredient in an active ingredient melt, or by dissolving the active ingredient and the amphiphilic polymer composition in a solvent and removing the solvent.

Preference is given to solid active substance compositions according to the invention which are obtained by drying the aqueous active substance compositions. These are solid materials, which usually occur in particulate form. Depending on the nature of the drying process, e.g. Powder or granules.

For drying, the volatiles, ie water and any solvents or volatile bases, are removed by conventional methods. Particularly noteworthy are the convective drying methods such as spray drying, spray fluidized bed drying, current drying, mill drying, belt drying and mixing of this drying method, by contact drying methods such as drum drying, chamber drying, thin-layer drying, drying in a paddle dryer or in a drum dryer, freeze drying, and radiation drying. Such processes are familiar to the person skilled in the art, for example from CM van't Land "Industrial Drying Equipment" Marcel Decker, Inc. 1991; O. Krischer, W. Käst, K. Kroll, "Trocknungstechnik", Vol. 1 to 3, Springer-Verlag 1978, 1959 and 1989; K. Masters, Spraydrying Handbook Longman Scientific and Technical; H. Uhlmann / Lothar Mörl, fluidized bed / - spray granules, Springerverlag 2000. Preferably, the drying of the aqueous active ingredient compositions at temperatures below the glass transition point of the polymer and in particular in the range of -20 ⁰ C to 100 ^c C.

Depending on the nature of the active substance or effect substance contained, the active substance or effect substance compositions according to the invention can be used in a manner comparable to conventional formulations of the particular active substance or effect substance. For example, active ingredient compositions containing at least one insecticidal, acaricidal or nematicidal active ingredient can be used to control harmful insects, acarids, or nematodes. If the active ingredient compositions according to the invention contain at least one fungicidal active ingredient, they can be used to combat harmful fungi. If the active ingredient compositions according to the invention contain a herbicidal active ingredient, they can be used for combating grass weeds and the like. Depending on the nature of the active ingredient, the compositions of the invention are used in particular for the protection of plants from attack by harmful organisms such as insects, acarina, nematodes or for protection against infestation with phytopathogenic fungi and the like, or in seed treatment or in material protection, for example for protection of lignocellulosic materials such as wood, against infestation with noxious insects, such as wood-destroying beetles, termites, ants and the like, or against infestation with wood-discoloring or wood-destroying fungi.

Of course, the compositions according to the invention can also be used in cosmetics or in medicine or in technical applications.

The invention will now be explained in more detail with reference to the following examples.

I. Preparation of the polymer composition:

1.1 Production Example 1:

a) 4000 g of a methyl-terminated polyethylene oxide (number average molecular weight 2000 daltons, KOH number 33 mg / g solid) and 573 g of a commercial biuret of hexamethylene diisocyanate (NCO content of 22%, viscosity at 23 ⁰ C of 4, 0 Pa.s) were dissolved in 4573 g of tetrahydrofuran and the solution heated to 60 ° C. 0.08 g of dibutyltin dilaurate was added and the reaction mixture was stirred while maintaining the temperature until the NCO content of the mixture had fallen to 0.46%.

b) 1500 g of tetrahydrofuran were heated under reflux. Within 2 hours, were simultaneously feed 1a, consisting of 1400.1 g of 2- (dimethylaminoethyl) methacrylate, 850.6 g of methyl methacrylate and 632.3 g of n-butyl methacrylate, and feed 1 b, consisting of 1500 g of tetrahydrofuran

(THF), 15.59 g of azobisisobutyronitrile (AIBN) and 58.42 g of mercaptoethanol, and the mixture was refluxed until the amount of monomer had dropped to less than 3% by weight of the originally used amount (determined by gas chromatography ). Then 6859 was added to the reaction mixture from step a and the mixture was stirred at 65 ° C until the NCO content had dropped to 0%. It was then diluted with 8573 g of tetrahydrofuran.

c) To the polymer solution from step b. Then you gave within 30 min

15 kg of water and distilled tetrahydrofuran under reduced pressure. In this way, a 30% strength by weight aqueous dispersion of the polymer was obtained. composition with an average particle size of 244 nm (determined by dynamic light scattering at pH = 7).

1.2 Production Example 2:

a) 1500 g of tetrahydrofuran were heated under reflux. Within 2 hours, were simultaneously feed 1a, consisting of 1112 g of 2-vinylpyridine, 1059.1 g of methyl methacrylate and 751, 9 g of n-butyl methacrylate, and feed 1b, consisting of 1500 g of tetrahydrofuran (THF), 18.59 g Azobisisobutyronitrile (AIBN) and 58.42 g of mercaptoethanol, and kept the mixture under so long

Reflux until the monomer level had dropped to less than 3 wt .-% of the original amount used (determined by gas chromatography). Then, 6859 was added to the reaction mixture from Example 1, step a and stirred at 65 ⁰ C until the NCO content had dropped to 0%. Subsequently, it was diluted with 8573 g of tetrahydrofuran.

b) 15 kg of water were added to the polymer solution thus obtained and distilled tetrahydrofuran under reduced pressure within 30 min. In this way, a 30% strength by weight aqueous dispersion of the polymer composition having an average particle size of 196 nm (determined by dynamic light scattering at pH = 7) was obtained.

1.3 Preparation Example 3: a) 1444 g of tetrahydrofuran (THF) were heated under reflux. In the course of two hours, feed 1a, consisting of 1631, 6 g of 3- (N ₁ N

Dimethylamino) propyl methacrylate (DMAPMA), 719.8 g of methyl methacrylate (MMA) and 460.7 g of 2-phenoxyethyl acrylate (POEA), and feed 1b, consisting of 1444 g of THF, 18.57 g of azobisisobutyronitrile (AIBN) and 58.36 g Mercaptoethanol was added and the mixture then heated under reflux until the amount of monomer to less than 3 wt .-% of the original used

Amount had dropped (determined by gas chromatography). Then 6859 g of the reaction mixture from Example 1, step a, was added and the mixture was subsequently heated to 65 ⁰ C until the isocyanate content had dropped to 0%. Finally, the reaction mixture was diluted with 7760 g of THF.

15 kg of water were added to the polymer solution thus obtained within 30 minutes and the THF was then distilled off under reduced pressure. In this way, a 30% by weight aqueous dispersion of Polymer composition having an average particle size of <20 nm (according to dynamic light scattering at pH = 7).

II. Preparation of aqueous active compound preparations according to the invention

11.1 Analytics:

The viscosities stated here were determined in a rotational viscometer according to DIN 53019-2.

The average particle diameter was determined by the method of static light scattering on a diluted sample of the aqueous active ingredient formulation at 20 ^° C.

To test the storage stability, the aqueous active compound compositions were stored for 2 weeks at room temperature for 2 weeks at 54 ⁰ C and 2 weeks at 5 ⁰ C. In addition, the active substance compositions were frozen and thawed again. Storage stability is given when neither sedimentation nor creaming is observed under these conditions.

11.2 General manufacturing instructions:

1. Solubilization method (liquid active ingredients and active ingredient melts):

10 g of active ingredient are stirred into 90 g of an aqueous dispersion of a polymer composition containing 30 g of polymer at a temperature at which the active ingredient is present as a low-viscosity melt (for example at 60 to 80 ^° C.). Depending on the viscosity of the polymer solution and the active ingredient melt, the stirring is carried out using a magnetic stirrer or an Ultraturrax. The time required for the equilibration equilibrium depends on the polymer composition and on the active substance and can take a few seconds but also a few hours. The solubilization equilibrium is reached when the active ingredient has distributed uniformly in the mixture and no change in the particle size is observed despite further energy input.

2nd phase inversion method:

13.33 g of a 15% solution of the liquid or solid in THF are mixed with 20 g of the 30% polymer solution in tetrahydrofuran. Then, while stirring, water is added and then the organic solvent is removed by distillation. It is added so much water, the resulting aqueous formulation is 10% by weight of active ingredient and 30% by weight of polymer.

3. Method of solid solution: 0, g of Pσlymerzusammensetzung (polymer content> 95 wt .-%) and

0.1 of the active ingredient are dissolved in about 20 ml of an organic solvent (preferably tetrahydrofuran, Drmethylfromamid). Subsequently, the solvent is completely removed (for example on a rotary evaporator) so that a solid solution of hydrophobic active ingredient and polymer composition remains. A buffered aqueous solution (100 ml, pH 6.8) is added and the mixture is stirred for 24 hours. After filtration, the solution is analyzed by means of HPLC (UV detector) and the concentration of the active ingredient is determined.

4. Jet precipitation:

A 30% aqueous polymer dispersion is mixed together with a 40% active / THF solution by means of two pumps in a mixing device via a mixing nozzle. The throughput of the polymer dispersion is 12 kg / h, the throughput of the THF solution is 3 kg / h, so that the total throughput is 15 kg / h. The mixing device is comparable to the apparatus described in "Handbook of Industrial Crystallization" (ASMyerson, 1993 Butworthworth-Heinemaπn, page 139, ISBN 0-7506-9155-7), giving a light yellow milky suspension with 8% active ingredient and 24% polymer, then THF and part of the water are removed by distillation to give 10% aqueous nanoparticulate formulation.

Active ingredient and 30% polymer is formed.

II.3 Formulation Example 1 Solubilization of Pyraclostrobin with Polymer Composition from Preparation Example 1b by the Phase Inversion Method (General Procedure 2)

13.33 g of a 15% strength solution of pyraclostrobin in THF were mixed with 20 g of polymer solution in THF (30% strength) from Example 1b. Water was added with stirring and the THF removed under reduced pressure. The amount of water was chosen so that the resulting aqueous formulation was 10% by weight.

% Active ingredient and 30% by weight of the polymer composition.

The active compound composition obtained was homogeneous, nearly visually transparent, and allowed to settle with water (both with demineralized water and water PT / EP2006 / 001106

50

10 ° dH) without sedimentation or crystallization of the active ingredient.

In an analogous manner, the other active ingredients listed in Table 1 can also be formulated.

Table 1

II.4 Formulation Example 2 Redispersion of a Solid Active Ingredient Formulation from Formulation Example 1

A 40% aqueous liquid formulation with pyraclostrobin (Formulation Example 2) was freeze-dried. The resulting solid formulation is stable for months (no drug crystals optically recognizable) and was diluted with water (both with deionized water and water 10 ° dH), without any sedimentation or crystallization of the drug occurred.

Formulation Example 3 Solubilization of Pyraclostrobin with Polymer Composition from Preparative Example 1b by the Solid Solution Method (General Procedure 3)

Pyraclostrobin was formulated according to the method of solid solution with polymer composition from preparation example 1b. The resulting solid solution is stable for at least several months (no drug crystals optically recognizable) and was diluted with water (both with demineralized water and water 10 ° dH), without any sedimentation or crystallization of the drug occurred.

II.6 Formulation Example 4 Solubilization of Pyraclostrobin with Polymer Composition from Preparation Example 1b According to the Solubilization Method (General Procedure 1) The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.

IU Formulation Example 5: Solubilization of Metconazole with Polymer Composition from Preparation Example 2b by the Phase Inversion Method (General Procedure 2)

13.33 g of a 15% solution of metconazole in THF were mixed together with 20 g of 30% polymer solution in THF from Example 1b. Water was added with stirring and the THF removed under reduced pressure. The amount of water was chosen so that the resulting aqueous formulation

10 wt .-% of active ingredient and 30 wt .-% of the polymer composition.

The active ingredient composition obtained was homogeneous, almost visually transparent, and allowed to dilute with water (both with demineralized water and water 10 ° dH) without sedimentation or crystallization of the product

Agent occurred.

II.8 Formulation Example 6: Redispersion of a solid formulation prepared from Formulation Example 5

A 40% liquid formulation with pyraclostrobin (Formulation Example 5) was freeze-dried. The resulting solid formulation is stable for months and allowed to dilute with water (both deionized water and water 10 ° dH) without sedimentation or crystallization of the drug.

II.9 Formulation Example 7: Solubilization of Pyraclostrobin with Polymer Composition from Preparation Example 2b by the Solid Solution Method (General Procedure 3)

Pyraclostrobin was solubilized by the method of solid solution with polymer composition from Preparation 2b. The resulting solid solution is stable for at least several months (no active substance crystals optically recognizable) and could be diluted with water (both with demineralized water and water 10 ° dH), without any sedimentation or crystallization of the active ingredient occurred.

10 Formulation Example 8 Solubilization of Pyraclostrobin with Polymer Composition from Preparation Example 2b by the Solubilization Method (General Procedure 1)

The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.

11.11 Formulation Example 9: Solubilization of Metconazole with Polymer Composition from Preparation Example 2b by the Phase Inversion Method (General Procedure 2)

13.33 g of a 15% solution of metconazole in tetrahydrofuran were together with 20 g of a 30% polymer solution in tetrahydrofuran from Example

1 b and a nonionic surfactant (see Table 3). Water was added with stirring and tetrahydrofuran removed under reduced pressure. The amount of water was chosen so that the resulting aqueous formulation contained 10% by weight of active ingredient and 30% by weight of the polymer composition.

Table 3: Drug formulations containing a low molecular weight compound

A: ethoxylated isotridecanol with a degree of ethoxylation of 8 B: ethoxylated C ₉ -C 18 alkanol with a degree of ethoxylation of 3

The active compound composition obtained was homogeneous, almost visually transparent, and could be diluted with water (both with demineralized water and water 10 ° dH), without any sedimentation or crystallization of the drug occurred. III Application Testing

111.1 Verification of fungicidal activity

The aqueous active substance composition from Formulation Example 5 (metconazole) was compared with a commercial formulation of the same active substance Metconazole with respect to its activity against brown rust (Puccinia recondita) on wheat plants in the greenhouse according to the following procedure:

Curative efficacy against wheat brown rust caused by Puccinia recondita

The active substance metconazole was prepared as a stock solution with a concentration of 64 ppm of active ingredient and then diluted with water to the active ingredient concentration given below (Table 4).

Leaves of potted wheat seedlings of the variety "Chancellor" were inoculated with a spore suspension of the brown rust {Puccinia recondita). Thereafter, the pots were placed in a high humidity chamber (90-95%) and 20-22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were sprayed the next day with an aqueous suspension in the drug concentration below, to drip point. The suspension was prepared as described above. After the spray coating had dried, the test plants were cultivated in the greenhouse at temperatures between 20 and 22.degree. C. and 65 to 70% relative humidity for 7 days. Then the extent of rust fungus development on the leaves was determined.

The results of the biological test are summarized in Table 4. The results show that polymer-stabilized drug has a fungicidal activity at the level of commercial products.

Table 4:

1) Composition of the conventional formulation:

200 g / l metconazole

70 g / l antifreeze

30 g / l nonionic dispersant

20 g / l anionic dispersant

2g / l thickener

2 g / l biocide in 1 l aqueous formulation

Claims

claims:

1. Polymer composition obtainable by reaction of

a) at least one polymer P1 which carries isocyanate-reactive functional groups R 1 and which is made up of ethylenically unsaturated monomers M 1, the monomers M 1 comprising more than 20% by weight, based on the total amount of monomers M 1, of monomers M 1 a have at least one functional group FG which comprises tertiary amino groups, imino groups, carboxyamide groups, nitrile groups,

Lactam groups, keto groups, aldehyde groups, urea groups, polyether groups, carboxyl groups, sulfonyl groups, hydroxysulfonyl groups and sulfonamide groups is selected,

c) with at least one isocyanate group-containing compound V, which has a functionality of at least 1.5 with respect to the isocyanate groups.

The polymer composition of claim 1, wherein the polymer P1 has a functionality F1 in the range of 0.3 to 3 with respect to the functional groups R 1.

3. Polymer composition according to claim 1 or 2, wherein the polymer P1:

a1)> 20 to 90 wt .-%, based on the total amount of the monomers M1, monoethylenically unsaturated monomers M1a; a2) from 10 to <80% by weight, based on the total amount of monomers M1,

Monomers M 1b, the water solubility at 25 ° C is less than 30 g / l which are different from the monomers M1a; and a3) 0 to 20 wt .-%, based on the total amount of the monomers M1, ethylenically unsaturated monomers M1c, which are different from the monomers M1a and M1 b comprises.

4. Polymer composition according to claim 3, wherein the monomers M1b are selected from monomers of the general formula I.

wherein

X is oxygen or a group NR ⁴ ;

R ¹ is C _r C ₂ -alkyl, C ₅ -C ₁₀ cycloalkyl, phenyl, phenyl-C |. -C ₄ alkyl or phenoxy

C 1 -C ₄ alkyl;

R ^{2 is} hydrogen or C _r C ₄ alkyl; R ^{3 is} hydrogen or C 1 -C ₄ alkyl; and

R _{4 is} hydrogen or C _r C ₄ alkyl.

5. A polymer composition according to claim 3 or 4, wherein the monomers M1a are selected from

Amides and CrC ^ alkyloxyalkylamides monoethylenically unsaturated

C ₃ -C ₈ monocarboxylic acids; monoethylenically unsaturated nitriles;

N-vinylamides of aliphatic, cycloaliphatic or aromatic carboxylic acids;

N-vinyl lactams having 5 to 7 ring atoms; vinyl-substituted nitrogen heteroaromatics; monoethylenically unsaturated monomers carrying urea groups;

Aldehyde- or keto-containing, monoethylenically unsaturated monomers; and monoethylenically unsaturated monomers having a primary, secondary or tertiary amino group.

A polymer composition according to any one of the preceding claims, wherein the polymer P1 has a number average molecular weight in the range of 500 to

20000 daltons.

7. A polymer composition according to any one of the preceding claims, wherein the poly-C ₂ -C ₄ alkylene ether P2 is at least 70 wt .-% of ethylene oxide groups.

8. A polymer composition according to any one of the preceding claims, wherein the poly-C ₂ -C ₄ alkylene ether P2 with respect to the functional groups R ₂ a Functionality F2 in the range of 0.5 to 3.0 has.

A polymer composition according to any one of the preceding claims wherein the poly-C ₂ -C ₄ alkylene ether P2 has a number average molecular weight in the range of 500 to 20,000 daltons.

10. Polymer composition according to one of the preceding claims, wherein the polymer P1 and the poly-C ₂ -C ₄ -alkylene ether P2 are used in a weight ratio P1: P2 in the range from 1:10 to 10: 1.

11. A process for the preparation of an amphiphilic polymer composition according to any one of the preceding claims, comprising the reaction

i) at least one polymer P1 and ii) at least one poly-C ₂ -C ₄ alkylene ether P2 with iii) at least one isocyanate group-containing compound V which has a functionality of at least 1.5 with respect to the isocyanate groups.

12. The method according to claim 11, wherein the polymer P1 and the poly-C ₂ -C ₄ - alkylene ether P2 is reacted successively with the compound V.

13. Process according to claim 11, wherein the polymer P1 and the poly-C ₂ -C ₄ -alkylene ether P2 are reacted in one step with the compound V.

14. Use of a polymer composition according to any one of claims 1 to 10 for the stabilization of active ingredients and / or effect substances which have a solubility in water at 25 ° C / 1013 mbar below 10 g / l, in an aqueous medium.

15. Use of a polymer composition according to any one of claims 1 to 10 for the preparation of formulations of active ingredients and / or effect substances which have a solubility in water at 25 ° C / 1013 mbar below 10 g / l.

16. Use of a polymer composition according to any one of claims 1 to 10 for the preparation of aqueous formulations of active ingredients and effect substances which have a solubility in water at 25 ° C / 1013 mbar below 10 g / l.

17. active ingredient composition comprising at least one active ingredient and / or effect substance, which in water at 25 ° C / 1013 mbar a solubility below 10 g / l and at least one polymer composition according to any one of claims 1 to 10.

18. Aqueous active ingredient composition comprising an aqueous medium as the continuous phase, at least one in the continuous phase solubilized or dispersed active ingredient and / or effect substance having a solubility in water at 25 ° C / 1013 mbar below 10 g / l, and at least one amphiphilic polymer composition according to any one of claims 1 to 10.

19. Active substance composition according to claim 18, wherein the active substances and effect substances contained in the aqueous phase form aggregates or particles whose mean particle size, determined by means of dynamic light scattering, does not exceed a value of 300 nm.

20. Active ingredient composition according to claim 17 to 19, containing the active ingredient and / or effect substance and the polymer composition in a weight ratio of 1:10 to 3: 1.

21. Active ingredient composition according to one of claims 17 to 20, with a content of volatile organic compounds of less than 10 wt .-%, based on the total weight of the composition.

22. A process for preparing an active ingredient composition according to any one of claims 17 to 21, comprising preparing a homogeneous, non-aqueous mixture comprising the amphiphilic polymer composition and at least one active ingredient and / or effect substance.

23. A process for preparing an aqueous drug composition according to any one of claims 18 to 20, comprising:

a) Preparation of a homogeneous, non-aqueous mixture consisting of amphiphilic polymer composition and active ingredient and / or effect substance, and

b) dispersing the mixture thus obtained with water.

24. A process for preparing an aqueous drug composition according to any one of claims 18 to 20, comprising: a) preparation of a solution of active ingredient and / or effect substance and optionally amphiphilic polymer composition in an organic solvent which has a boiling point below that of water and

b) mixing the solution of the active ingredient and / or effect substance with water or an aqueous solution of the amphiphilic copolymer and

c) removal of the organic solvent.

25. A process for preparing an aqueous active substance composition according to any one of claims 18 to 21, comprising incorporating the active ingredient and / or the effect substance in an aqueous solution of the amphiphilic polymer composition at a temperature above the melting temperature of the active ingredient.

26. A solid active substance composition comprising at least one amphiphilic polymer composition according to any one of claims 1 to 10 and at least one in the polymer composition finely divided active ingredient and / or effect substance which in water at 25 "C / 1013 mbar a solubility below 10 g / l has.

A solid drug composition according to claim 26 containing the active ingredient and / or effect substance and the amphiphilic polymer composition in a weight ratio of 1:10 to 3: 1.

28. A solid active ingredient composition obtainable by drying a liquid, in particular an active ingredient composition according to any one of claims 17 to 21.