WO2021115916A1 - Suspension concentrate - Google Patents

Abstract

The invention relates to suspension concentrates (SC) for crop protection active compounds, a method for the manufacture of such suspension concentrates and suspensions, and their use for combating pests.

Description

Suspension concentrate

The invention relates to storage stable suspension concentrates (SC) for crop protection active compounds, a method for the manufacture of such suspension concentrates and suspensions, and their use for combating pests.

Suspension concentrates (SC) are widely used formulations in crop protection. They have grown in popularity due to benefits such as absence of dust and flammable solvents as well as ease of use. Despite of said benefits, there are also some disadvantages. The most common once are the storage instability because of gelling, caking, settling and crystal growth. When improving these physical properties, the bioavailability of the suspended active ingredient might suffer. However, it is always desirable to increase the biological activity of the formulation. Hence, the main task to be solved when preparing SCs is to find a balance between efficacy and physicochemical stability of the SCs. Additionally, in view of avoiding unnecessary packing material, it is desirable to develop concentrated formulations.

Therefore, the problem of the present invention was to provide a suspension concentrate containing pesticidal active ingredients with an increased efficacy and good storage stability.

This problem was solved by a suspension concentrate comprising

I) a pesticidal active ingredient having the solubility in water of not more than 1 g/l at 25°C,

II) a hyperbranched polymer comprising a) a hyperbranched polycondensate with hydroxyl and/or amino end groups condensed to b) one or more linkers connected to c1) one or more polyethylene glycol monomethyl ethers and c2) one or more poly(C2-C3)alkylene glycol mono-(C8-C22)-alkyl ethers, wherein the weight ratio of components d) : c2) is from 9 : 1 to 1 : 9;

III) a (Cs-C22)-fatty alcohol alkoxylate.

SC formulations comprising hyperbranched polymers are known, for example, from US 9,801,372.

The amount of the component (I) in the composition is usually from 1 to 40% by weight based on the total weight of the composition, preferably 1 to 35% by weight, more preferably 5 to 30% by weight, most preferably 5 to 25% by weight, in particular 5 to 20% by weight.

The amount of the component (II) in the composition is usually from 5 to 30% by weight based on the total weight of the composition, preferably 5 to 25% by weight, more preferably 8 to 25% by weight, most preferably 10 to 25% by weight, in particular 10 to 20% by weight.

The amount of the component (III) in the composition is usually from 1 to 15% by weight based on the total weight of the composition, preferably 1 to 12% by weight, more preferably 1 to 10% by weight, most preferably 1 to 8% by weight, in particular 1 to 6% by weight. The weight ratio of the component (I) to component (II) is usually in the range from 1:25 to 25:1, preferably 1:10 to 10:1, more preferably 1:5 to 5:1.

The weight ratio of the component (III) to component (II) is usually in the range from 1:10 to 10:1, preferably 1:8 to 8:1, more preferably 1:5 to 5:1.

The present invention entails a series of advantages. Particularly, the high pesticide concentrations in the concentrate can be employed. The concentrate, although containing large amounts of the active ingredients in suspended form, exhibit good physical and chemical stability over prolonged storage times. Thus, neither significant agglomeration of the active ingredients occurs, nor significant crystal growth is observed. A stable suspension forms spontaneously upon dilution of the concentrate with water. Moreover, the formulations of the invention show outstanding pesticidal activity.

The SC according to the present invention is preferably an aqueous SC.

As component (I) the composition may contain one, two, three, four or more water insoluble pesticidal active ingredients

The term “water-insoluble” means that the pesticidal active ingredient is soluble in water to not more than 1 g/l, preferably not more than 200 mg/I and in particular to not more than 50 mg/I at 25°C. Using simple preliminary experiments, the skilled person can select a pesticidal active ingredient with a suitable water-solubility.

The term "pesticidal active ingredients" (also referred to as pesticides) refers to at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators. The term "insecticide" as used herein encompasses compounds with insecticidal and/or accaricidal activity. Preferred pesticides are fungicides, insecticides and herbicides, especially fungicides. Mixtures of pesticides from two or more of the abovementioned classes can also be used. The person skilled in the art is familiar with such pesticides, which can be found, for example, in The Pesticide Manual, 16^th Ed. (2012), The British Crop Protection Council, London.

Suitable fungicides are, e.g., fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic compounds, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oxi mi noacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenyl- pyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles.

Suitable insecticides are, e.g., insecticides from the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof.

Suitable herbicides are, e.g., herbicides of the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.

In a preferred embodiment, the pesticidal active ingredient is a fungicide.

According to one specific embodiment, the fungicide is selected from triazole fungicides, such as azaconazole, bitertanol, bromuconazole , cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 2 (2,4-difluorophenyl)-1,1- difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2 pyridyl]propan-2-ol, 2-(2,4- difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2- ol, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3- pyridyljoxyjbenzonitrile, ipfentrifluconazole, mefentrifluconazole, 2-(chloromethyl)-2-methyl-5-(p- tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol; preferably epoxiconazole, mefentrifluconazole, prothioconazole; more preferably mefentrifluconazole.

According to another specific embodiment, the fungicide is selected from strobilurine fungicides, such as azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin; preferably azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, more preferably azoxystrobin. According to another specific embodiment, the composition comprises two different fungicides. One fungicide is preferably selected from the triazole fungicides as defined above; more preferably from epoxiconazole, mefentrifluconazole, prothioconazole; most preferably mefentrifluconazole. The second one is preferably selected from strobilirine fungicides as defined above, more preferably from azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, most preferably azoxystrobin. According to a particular embodiment, the composition comprises mefentrifluconazole and azoxystrobin.

The pesticides that may be used according to the invention, their preparation and their biological activity e. g. against harmful fungi, pests or weed is known (cf. : http://www.alanwood.net/pesticides/); these substances are mostly commercially available.

The active ingredient is present in solid particulate form in the composition. The particles may be crystalline or amorphous. The particle size of the suspended particles is in the range which is typical of suspension concentrates. As a rule, the particles have a mean particle diameter, herein also termed D50 value, in the range from 0.5 to 20 pm, in particular in the range from 0.6 to 10 pm, specifically in the range from 0.8 to 5 pm. The Dso-value is defined as the value that is above the diameters of 50% by weight of the particles and below the diameters of 50% by weight of the particles. Preferably, at least 80% by weight, in particular at least 90% by weight, of the particles have particle sizes in the stated ranges. A particle size that is not exceeded by the diameters of at least 90% by weight of the particles is herein also termed the Dgo-value. In general, the Dgo-value of the suspended a.i. particles of the formulation according to the invention will not exceed 20 pm, preferably not exceed 10 pm and in particular not exceed 6 pm. Advantageously, at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight of the particles have a particle diameter of below 8 pm or even below 6 pm. The particle size of the active substance particles can be determined by conventional methods such as light-scattering.

As component (II) the composition comprises a hyperbranched polymer. Such hyperbranched polymers and their preparation are known from WO 2016/102203. The hyperbranched polymers (II) comprise, preferably consist of, a core, which is a hyperbranched polycondensate a) with hydroxyl and/or amino end groups, and of a shell, which is a mixture of one or more polyethylene glycol monomethyl ethers (MPEG) (d) and one or more poly(C2-Cs)alkylene glycol mono-(C8-C22)-alkyl ethers (FAPAG) (c2) in a weight ratio of 1 : 9 to 9 : 1. Core and shell are connected by a linker (b) which is condensed to the hydroxyl and/or amino groups of the polycondensate (a) and the hydroxyl end groups of the MPEG/FAPAG mixture (d)/(c2).

“Hyperbranched” in the context of the invention means that the degree of branching (DB), in other words the ratio of the sum of the average number of dendritic linkages plus the average number of end groups to the sum of the average number of dendritic and linear linkages plus the average number of end groups, per molecule, multiplied by 100, is 10% to 99.9%, preferably 20% to 99%, more preferably 20% to 95%.

“Dendrimeric” in the context of the present invention means that the degree of branching is 99.9% - 100%. For the definition of the degree of branching see H. Frey et al., Acta Polym.

1997, 48, 30. Hvperbranched polvcondensates (a)

The hyperbranched polycondensate (a) is preferably selected from the group consisting of hyperbranched polycarbonates, polyesters, polyimides, polyurethanes, polyureas, polyamides, polythioureas, polyethers, polyestercarbonates, polyethercarbonates, polyetheresters, polyesteramides, polyesteramines, polyetherestercarbonates and polyetherurethanecarbonates. Such compounds and the preparation thereof are described, for example, in WO 2009/021986.

Preferred as hyperbranched polycondensates (a) are hyperbranched polycarbonates (a1), polyesters (a2), polyimides (a3), polyurethanes (a4) and polyureas (a5). More preferred are hyperbranched polycarbonates (a1), polyesters (a2) and polyimides (a3). Even more preferred are hyperbranched polycarbonates (a1) and polyesters (a2). Hyperbranched polyesters (a2) are particularly preferred.

By hyperbranched polycondensates or polymers for the purposes of this invention are meant non-crosslinked macromolecules having hydroxyl and/or amino end groups, which may be both structurally and molecularly nonuniform. On the one hand they may be synthesized starting from a central molecule in the same way as for dendrimers but, in contrast to the latter, with a nonuniform chain length of the branches. Hyperbranched polycondensates/polymers are therefore to be differentiated from dendrimers (US 6,399,048). For the purposes of the invention, hyperbranched polycondensates/polymers do not comprise dendrimers. On the other hand, the hyperbranched polymers may also be of linear construction, with functional, branched side groups, or else, as a combination of the two extremes, may include linear and branched molecule moieties. For the definition of dendrimers and hyperbranched polymers see also P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al. , Chem. Eur. J. 2000, 6, 2499.

“Noncrosslinked” for the purposes of this specification means that the degree of crosslinking is less than 15% by weight, preferably less than 10% by weight, determined via the insoluble fraction of the polymer. The insoluble fraction of the polycondensate is determined by four-hour extraction with the same solvent as used for the gel permeation chromatography for determining the molecular weight distribution of the polymers, i.e. , tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol, according to which solvent has the better solvency for the polycondensate, in a Soxhlet apparatus and, after drying of the residue to constant weight, by weighing of the residue remaining.

Polycarbonates (a1)

In pne embpdiment the hyperbranched pelycendensate (a) is a hyperbranched pelycarbenate. The hyperbranched pelycarbenate is typically cbtainable by a) preparing a ccndensaticn product (K) by reacting an crganic carbcnate (A) cr a phesgene derivative with an alcchcl (B1) which has at least three hydroxyl groups, and b) intermclecularly ccnverting K tc the hyperbranched pelycarbenate, the quantitative ratio of the OH groups to the carbonate or phosgene groups being selected such that K has an average of either i) one carbonate or carbamoyl chloride group and more than one OH group, or ii) one OH group and more than one carbonate or carbamoyl group. The polycarbonate is preferably obtained in this way.

The condensation product (K) can be prepared using an organic carbonate (A) or a phosgene derivative. Examples of suitable phosgene derivatives are phosgene, diphosgene or triphosgene, preferably phosgene. It is preferred to use an organic carbonate (A). The hyperbranched polycarbonate preferably comprises an organic carbonate (A) in polymerized form.

The radicals R in the organic carbonates (A) of the general formula RO[(CO)0]_nR that are used as starting material are each independently of one another a straight-chain or branched aliphatic, aromatic/aliphatic (araliphatic) or aromatic hydrocarbon radical having 1 to 20 C atoms. The two radicals R may also be joined to one another to form a ring. The two radicals R may be the same or different; they are preferably the same. The radical in question is preferably an aliphatic hydrocarbon radical and more preferably a straight-chain or branched alkyl radical having 1 to 5 C atoms, or a substituted or unsubstituted phenyl radical. R in this case is a straight-chain or branched, preferably straight-chain (cyclo)aliphatic, aromatic/aliphatic or aromatic, preferably (cyclo)aliphatic or aromatic, more preferably aliphatic hydrocarbon radical having 1 to 20 C atoms, preferably 1 to 12, more preferably 1 to 6, and very preferably 1 to 4 carbon atoms. Examples of such radicals are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n- octadecyl, n-eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, phenyl, o- or p-tolyl or naphthyl. Methyl, ethyl, n-butyl, and phenyl are preferred. These radicals R may be the same or different; they are preferably the same. The radicals R may also be joined to one another to form a ring. Examples of divalent radicals R of this kind are 1,2-ethylene, 1,2- propylene, and 1,3-propylene. Generally speaking, n is an integer from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2. The carbonates may preferably be simple carbonates of the general formula RO(CO)OR, i.e. n in this case is 1.

Examples of suitable carbonates comprise aliphatic, aromatic/aliphatic or aromatic carbonates such as ethylene carbonate, 1,2- or 1,3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethyl phenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or didodecyl carbonate. Examples of carbonates in which n is greater than 1 comprise dialkyl dicarbonates, such as di-tert-butyl dicarbonate, or dialkyl tricarbonates such as di-tert-butyl tricarbonate. One preferred aromatic carbonate is diphenyl carbonate. Preference is given to aliphatic carbonates, more particularly those in which the radicals comprise 1 to 5 C atoms, such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate or diisobutyl carbonate, for example. Diethyl carbonate is especially preferred.

The hyperbranched polycarbonate preferably comprises an alcohol (B1) in polymerized form. The alcohol (B1) which has at least three hydroxyl groups is usually an aliphatic or aromatic alcohol, or a mixture or two or more different alcohols of this kind. The alcohol (B1) may be branched or unbranched, substituted or unsubstituted, and have 3 to 26 carbon atoms. It is preferably an aliphatic alcohol. Examples of compounds having at least three OH groups comprise glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, tris(hydroxymethyl)amine, tris(hydroxyl- ethyl)amine, tris(hydroxypropyl)amine, pentaerythritol, diglycerol, triglycerol, polyglycerols, bis(trimethylolpropane), tris(hydroxymethyl) isocyanurate, tris(hydroxyethyl) isocyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1,1,1-tris(4’-hydroxyphenyl)methane, 1,1,1- tris(4’-hydroxyphenyl)ethane, sugars, for example glucose, sugar derivatives, for example sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, or polyesterol.

Preferably, B1 is a trifunctional or higher-functionality polyetherol based on alcohols which have at least three OH groups, and C2-C24 alkylene oxide. The polyetherol comprises usually one to 30, preferably one to 20, more preferably one to 10 and most preferably one to eight molecules of ethylene oxide and/or propylene oxide and/or isobutylene oxide per hydroxyl group. The hyperbranched polycarbonate preferably comprises an alcohol (B1) which is a trifunctional or higher-functionality polyetherol based on alcohols which have at least three OH groups, and C3- C24 alkylene oxide. Suitable alcohols which have at least three OH groups are as described above, preferably glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,3- hexanetriol, 1,2,4-hexanetriol, pentaerythritol, more preferably glycerol or trimethylolpropane. Preferred C3-C24 alkylene oxides include propylene oxide, butylene oxide, pentylene oxide and mixtures thereof, more preferably propylene oxide. The trifunctional or higher-functionality polyetherols usually comprise at least one to 30, preferably two to 30, more preferably three to 20 C3-C24 alkylene oxide molecules in polymerized form. A particularly preferred alcohol (B1) is a trifunctional polyetherol based on glycerol, trimethylolethane, trimethylolpropane, 1,2,4- butanetriol and/or pentaerythritol, and propylene oxide, where the polyetherol comprises at least three, preferably three to 30, more preferably three to 20, molecules of propylene oxide in polymerized form. Polyetherols (B1) are commercially available, e.g. under the Lupranol^® marks, such as Lupranol^® 3902 and 9319, from BASF SE.

In addition to the alcohol (B1), the polycarbonate may have a difunctional alcohol (B2) as a forming component, with the proviso that the mean OH functionality of all alcohols B used together is greater than 2. The alcohols (B1) and (B2) are referred to here together as (B). Suitable difunctional alcohols B2 include diethylene glycol, triethylene glycol, 1,2- and 1,3- propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3- and 1,4- butanediol, 1,2-, 1,3- and 1,5-pentanediol, 1,6-hexanediol, 1,2- or 1,3-cyclopentanediol, 1,2-,

1,3- or 1,4-cyclohexanediol, 1,1-, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, bis(4- hydroxycyclohexyl) methane, bis(4-hydroxycyclohexyl)ethane, 2,2-bis(4- hydroxycyclohexyl)propane, 1 ,T-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, resorcinol, hydroquinone, 4,4’-dihydroxybiphenyl, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(hydroxymethyl)benzene, bis(hydroxylmethyl)toluene, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-bis(p- hydroxyphenyl)cyclohexane, dihydroxybenzophenone, difunctional polyetherpolyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, polytetrahydrofuran having a molar mass of 162 to 2000, polycaprolactone or polyesterols based on diols and dicarboxylic acids. Preferred difunctional alcohols (B2) are difunctional polyetherpolyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, and polyesterols based on diols and dicarboxylic acids.

The diols serve for fine adjustment of the properties of the polycarbonate. If difunctional alcohols are used, the ratio of difunctional alcohols (B2) to the at least trifunctional alcohols (B1) is fixed by the person skilled in the art according to the desired properties of the polycarbonate. In general, the amount of the alcohol(s) (B2) is 0 to 50 mol% based on the total amount of all alcohols (B1) and (B2) together. The amount is preferably 0 to 35 mol%, more preferably 0 to 25 mol% and most preferably 0 to 10 mol%. In one preferred embodiment the polycondensate (a1) does not contain a difunctional alcohol (B2). In another embodiment the polycondensate (a1) comprises 0.5 to 10 mol% of a difunctional alcohol (B2).

The reaction of phosgene, diphosgene or triphosgene with the alcohol or alcohol mixture is generally effected with elimination of hydrogen chloride; the reaction of the carbonates with the alcohol or alcohol mixture to give the inventive high-functionality highly branched polycarbonate is effected with elimination of the monofunctional alcohol or phenol from the carbonate molecule.

After this reaction, i.e. without any further modification, the hyperbranched polycarbonate has high-functionality termination with hydroxyl groups and with carbonate groups or carbamoyl chloride groups. A high-functionality polycarbonate is understood in the context of this invention to mean a product which, as well as the carbonate groups which form the polymer skeleton, additionally has, in terminal or lateral position, at least three, preferably at least four and more preferably at least six functional groups. The functional groups are carbonate groups or carbamoyl chloride groups and/or OH groups. There is in principle no upper limit in the number of terminal or lateral functional groups, but products with a very high number of functional groups may have undesired properties, for example high viscosity or poor solubility. The polycarbonates of the present invention usually have not more than 500 terminal or lateral functional groups, preferably not more than 100 terminal or lateral functional groups.

In the preparation of the high-functionality polycarbonates, it is necessary to adjust the ratio of the compounds comprising OH groups to phosgene or carbonate (A) such that the resulting simplest condensation product (known hereinafter as condensation product (K)) comprises an average of either i) one carbonate or carbamoyl chloride group and more than one OH group or ii) one OH group and more than one carbonate or carbamoyl chloride group, preferably an average of either i) one carbonate or carbamoyl chloride group and at least two OH groups or ii) one OH group and at least two carbonate or carbamoyl chloride groups.

In a further embodiment, for fine adjustment of the properties of the polycarbonate, at least one difunctional carbonyl-reactive compound (A1) is used. This is understood to mean compounds which have two carbonate and/or carboxyl groups. Carboxyl groups may be carboxylic acids, carbonyl chlorides, carboxylic anhydrides or carboxylic esters, preferably carboxylic anhydrides or carboxylic esters and more preferably carboxylic esters. If such difunctional compounds (A1) are used, the ratio of (A1) to the carbonates or phosgenes (A) is fixed by the person skilled in the art according to the desired properties of the polycarbonate. In general, the amount of the difunctional compound(s) (A1) is 0 to 40 mol% based on the total amount of all carbo- nates/phosgenes (A) and compounds (A1) together. Preferably the amount is 0 to 35 mol%, more preferably 0 to 25 mol%, and very preferably 0 to 10 mol%. Examples of compounds (A1) are dicarbonates or dicarbamoyl chlorides of diols, examples of which are ethylene glycol, 1,2- propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2- ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 1,2-, 1,3- or 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, bis(4- hydroxycyclohexane)isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexane- diol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2-ethyl-1,3-hexanediol, 2,4-di- ethyloctane-1,3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2- bis(4-hydroxycyclohexyl)propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, and 1,2-, 1,3- or 1,4-cyclohexanediol. These compounds may be prepared, for example, by reacting said diols with an excess of, for example, the above-recited carbonates RO(CO)OR or chlorocarbonic esters, so that the dicarbonates thus obtained are substituted on both sides by groups RO(CO)-. A further possibility is to react the diols first with phosgene to give the corresponding chlorocarbonic esters of the diols, and then to react these esters with alcohols.

Further compounds (A1) are dicarboxylic acids, esters of dicarboxylic acids, preferably the methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl or tert-butyl esters, more preferably the methyl, ethyl or n-butyl esters. Examples of dicarboxylic acids of this kind are oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, 1 ,4-cyclohexane- dicarboxylic acid or tetrahydrophthalic acid, suberic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, dimeric fatty acids, isomers thereof and hydrogenation products thereof.

The simplest structure of the condensation product (K), illustrated using, as example, the reaction of a carbonate (A) with a dialcohol or polyalcohol (B), produces the arrangement XY_m or Y_mX, X being a carbonate or carbamoyl group, Y a hydroxyl group, and m generally an integer greater than 1 to 6, preferably greater than 1 to 4, more preferably greater than 1 to 3. The reactive group, which results as a single group, is generally referred to below as “focal group”.

Where, for example, in the preparation of the simplest condensation product (K) from a carbonate and a dihydric alcohol, the molar reaction ratio is 1:1, then the result on average is a molecule of type XY, illustrated by the general formula (I).

In the case of the preparation of the condensation product (K) from a carbonate and a trihydric alcohol with a molar reaction ratio of 1:1, the result on average is a molecule of type XY2, illustrated by the general formula (II). The focal group here is a carbonate group. In the preparation of the condensation product (K) from a carbonate and a tetrahydric alcohol, again with the molar reaction ratio 1:1, the result on average is a molecule of type XY3, illustrated by the general formula (III). The focal group here is a carbonate group.

In the formulae (I) to (III) R is as defined at the outset and R¹ is an aliphatic or aromatic radical. The condensation product (K) can also be prepared, for example, from a carbonate and a tri- hydric alcohol, illustrated by the general formula (IV), where the reaction ratio on a molar basis is 2:1. Here the result on average is a molecule of type X2Y, the focal group here being an OH group. In the formula (IV) the definitions of R and R¹ are the same as above in formulae (I) to

Where difunctional compounds, e.g., a dicarbonate or a diol, are additionally added to the components, this produces an extension of the chains, as illustrated for example in the general formula (V). The result again is on average a molecule of type XY2, the focal group being a carbonate group.

In formula (V) R² is an aliphatic or aromatic radical while R and R¹ are defined as described above.

It is also possible to use two or more condensation products (K) for the synthesis. In this case it is possible on the one hand to use two or more alcohols and/or two or more carbonates. Furthermore, through the choice of the ratio of the alcohols and carbonates or phosgenes used, it is possible to obtain mixtures of different condensation products with different structure. This may be exemplified taking, as example, the reaction of a carbonate with a trihydric alcohol. If the starting products are used in a 1:1 ratio, as depicted in (II), a molecule XY2 is obtained. If the starting products are used in a 2:1 ratio, as illustrated in (IV), the result is a molecule X2Y. With a ratio between 1:1 and 2:1 a mixture of molecules XY₂ and X₂Y is obtained.

The stoichiometry of components (A) and (B) is generally chosen such that the resultant condensation product (K) contains either one carbonate or carbamoyl chloride group and more than one OH group, or one OH group and more than one carbonate or carbamoyl chloride group. This is achieved in the first case by a stoichiometry of 1 mol of carbonate groups: >2 mol of OH groups, for example, a stoichiometry of 1:2.1 to 8, preferably 1:2.2 to 6, more preferably 1:2.5 to 4, and very preferably 1:2.8 to 3.5. In the second case it is achieved by a stoichiometry of more than 1 mol of carbonate groups: <1 mol of OH groups, for example, a stoichiometry of 1:0.1 to 0.48, preferably 1:0.15 to 0.45, more preferably 1:0.25 to 0.4, and very preferably 1:0.28 to 0.35.

The simple condensation products (K) described exemplarily in formulae (I) - (V) preferably undergo immediate intermolecular further reaction to form high-functionality polycondensation products, preferably polycondensation products (P).

In view of the nature of the condensation products (K) it is possible that the condensation reaction may result in polycondensation products (P) having different structures, with branches but no crosslinks. Furthermore, the polycondensation products (P) ideally contain either a carbonate or carbamoyl chloride focal group and more than two OH groups, or else an OH focal group and more than two carbonate or carbamoyl chloride groups. The number of reactive groups depends on the nature of the condensation products (K) employed and on the degree of polycondensation.

The hyperbranched polycarbonates obtainable as described above generally have a glass transition temperature of less than 50°C, preferably less than 30 and more preferably less than 10°C. The OH number is usually at least 30 mg KOH/g, preferably between 50 and 500 mg/g. The weight-average molar weight Mw is usually between 1000 and 150000, preferably from 1500 to 100000 g/mol, the number-average molar weight Mn between 500 and 50 000, preferably between 1000 and 40000 g/mol. The hyperbranched polycarbonate is usually not soluble or dispersible in water, i.e. , it is not possible to prepare a clear (i.e. , devoid of particles visible to the naked eye) aqueous solution or dispersion.

Polyesters (a2)

In a further preferred embodiment the hyperbranched polymer is a hyperbranched polyester. In a known manner, the polyesters have ester linkages. In one preferred embodiment, the polymers comprise, as structural units, in each case at least one hydrophobic dicarboxylic acid unit and at least one trifunctional alcohol. They may additionally comprise further structural units. The hyperbranched polyester is usually soluble or dispersible in water, which means that it is possible to prepare a clear (i.e. without particles discernible to the naked eye) aqueous solution or dispersion.

The polyester is preferably based on a hydrophobic dicarboxylic acid which is an aliphatic C10- C32 dicarboxylic acid, a dicarboxylic acid having a polyisobutylene group and/or a succinic acid unit having a C3-C40 group. In a preferred embodiment, the hydrophobic dicarboxylic acid is an aliphatic C10-C32 dicarboxylic acid. In a further preferred embodiment, the hydrophobic dicarboxylic acid is a dicarboxylic acid having a polyisobutylene group. In a further preferred embodiment, the hydrophobic dicarboxylic acid is a succinic acid unit having a C3-C40 group. In a further preferred embodiment, the hydrophobic dicarboxylic acid is a dicarboxylic acid having a polyisobutylene group and/or a succinic acid unit having a C3-C40 group.

A suitable hydrophobic dicarboxylic acid is an aliphatic C10-C32 dicarboxylic acid. Preference is given to sebacic acid, a,w-undecanedicarboxylic acid, a,w-dodecanedicarboxylic acid, tridecanedicarboxylic acid (brassylic acid). Sebacic acid is especially preferred.

Another suitable hydrophobic dicarboxylic acid is a dicarboxylic acid having a polyisobutylene group (also referred to hereinafter as "PIB diacid"). In this connection, a "dicarboxylic acid having a polyisobutylene group" has at least two dicarboxylic acid groups, at least two dicarboxylic ester groups or at least one dicarboxylic anhydride group (it preferably has one dicarboxylic anhydride group). Such PIB diacids are obtainable by reacting polyisobutylene with an enophile. In a preferred embodiment, the products are 1 : 1 (mol/mol) reaction products of an ene reaction of a polyisobutylene and of the enophile. The PIB diacid is prepared by the processes known to those skilled in the art and preferably as described in German laid-open specifications DE-A 195 19042, preferably from page 2 line 39 to page 4 line 2 and more preferably from page 3 line 35 to 58, and DE-A 43 19671 , preferably from page 2 line 30 to line 68, and DE-A 43 19672, preferably from page 2 line 44 to page 3 line 19, described processes for reacting polyisobutylenes with enophiles. The polyisobutylenes are preferably those which have to an extent of at least 60 mol% end groups formed from vinyl isomer and/or vinylidene isomer.

To synthesize the hyperbranched polyesters, it is possible to use succinic acid substituted in the manner described. The succinic acid may preferably be used, however, in the form of activated derivatives, especially in the form of halides, esters or anhydrides.

Derivatives are especially the relevant anhydrides in monomeric or else polymeric form, mono- or dialkyl esters, preferably mono- or di-CrC4-alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and also mono- and divinyl esters and mixed esters, preferably mixed esters with different CrC4-alkyl components, more preferably mixed methyl ethyl esters. Particular preference is given to using succinic anhydrides as the starting material. In addition to the high reactivity of the anhydrides, the use of the anhydrides has the advantage that alkenylsuccinic anhydrides can be prepared in a particularly simple and inexpensive manner by reacting maleic anhydrides with olefins which have a hydrogen atom in the allyl position (the so- called ene reaction). Reaction of linear a-olefins can provide alkenylsuccinic anhydrides with n- alkenyl radicals; isomerized olefins with nonterminal double bonds give rise to succinic anhydrides substituted by isoalkenyl radicals. The olefins used may also be reactive oligo- or polyolefins, though reactive polyisobutenes are preferably not used. The preparation of alkenyl succinic anhydrides (also known as ASA) by means of the ene reaction is described in detail, for example, in WO 97/23474 or DE 195 19042 and the literature cited therein.

Succinic anhydrides substituted by alkenyl groups which are used with preference are n- or isohexenylsuccinic anhydride, n- or isoheptenylsuccinic anhydride, n- or isooctenylsuccinic anhydride, n- or isooctadienylsuccinic anhydride, n- or isononenylsuccinic anhydride, n- or isodecenylsuccinic anhydride, n- or isododecenylsuccinic anhydride (DDSA), n- or isotetra- decenylsuccinic anhydride, n- or isohexadecenylsuccinic anhydride, n- or isooctadecenyl- succinic anhydride, tetrapropenylsuccinic anhydride, 2-dodecenyl-3-tetradecenylsuccinic anhydride. It will be appreciated that it is also possible to use mixtures of different substituted anhydrides.

Particularly preferred products are n- or isooctenylsuccinic anhydride, n- or isododecenyl succinic anhydride (DDSA), n- or isotetradecenylsuccinic anhydride, n- or isohexadecenyl succinic anhydride, n- or isooctadecenylsuccinic anhydride, tetrapropenylsuccinic anhydride or mixtures of the products mentioned. Very particular preference is given to n- or isohexadecen ylsuccinic anhydride, n- or isooctadecenylsuccinic anhydride, or mixtures thereof.

The alkenylsuccinic acids or derivatives or mixtures thereof can also be used in a mixture with alkylsuccinic acids or derivatives thereof.

To prepare the hyperbranched polyesters, at least one hydrophobic dicarboxylic acid is reacted with at least one trifunctional alcohol, the ratio of the reactive groups in the reaction mixture being selected such that a molar ratio of OH groups to carboxyl groups or derivatives thereof of 5:1 to 1:5, preferably of 4:1 to 1:4, more preferably of 3:1 to 1:3 and most preferably of 2:1 to 1:2 is established. When mixtures of hydrophobic aliphatic C10-C32 dicarboxylic acids and/or dicarboxylic acids having polyisobutylene groups and/or succinic acid units having a C3-C40 group are used, the stoichiometry of OH groups to carboxyl groups is usually maintained as described above.

Trifunctional alcohols are understood to mean alcohols with at least three alcohol groups. Suitable trifunctional alcohols are glycerol, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, or an alkoxylated, preferably ethoxylated or propoxy- lated) derivative thereof. It will be appreciated that it is also possible to use mixtures of a plurality of different trifunctional alcohols. Preferred trifunctional alcohols are glycerol, trimethylolpropane and pentaerythritol. Very particular preference is given to glycerol and trimethylolpropane. Alkoxylated derivatives of glycerol, trimethylolethane, trimethylolpropane, bis(trimethylol- propane), pentaerythritol can be obtained in a manner known in principle by alkoxylating the alcohols with alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, and/or pentylene oxide. The mixed alkoxylated polyetherols may be copolymers in which, for example, different alkylene oxide units are distributed randomly in the chain, or they may be block copolymers.

The alkoxylated derivative of glycerol, trimethylolethane, trimethylolpropane, bis(trimethylol- propane) or pentaerythritol is preferably alkoxylated with 1.1 to 20 alkylene oxide units, preferably ethylene oxide and/or propylene oxide units. The alkoxylated derivative of glycerol, trimethylolpropane or pentaerythritol is most preferably alkoxylated with 1.1 to 20 propylene oxide units.

In further embodiments it is possible to use further components to synthesize the hyperbranched polymers used in accordance with the invention. Such components can be used to influence the properties of the polymers and adjust them optimally for the desired purpose.

For instance, it is possible to use further di- or polyfunctional carboxylic acids. Examples of further carboxylic acids comprise malonic acid, succinic acid, glutaric acid, adipic acid, 1,2-, 1,3- or 1 ,4-cyclohexanedicarboxylic acid (hexahydrophthalic acids), phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, especially the anhydrides or esters thereof. The amount of such further carboxylic acids should, however, generally not exceed 50 mol% based on the amount of all carboxylic acids used (i.e. sum of hydrophobic dicarboxylic acids and further di- or polyfunctional carboxylic acids) together.

In addition, as well as the trifunctional alcohols, it is also possible to use difunctional aliphatic, cycloaliphatic, araliphatic or aromatic diols. The suitable selection of dihydric alcohols can influence the properties of the polyesters. Examples of suitable diols are ethylene glycol, 1,2- propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-bis(hydroxymethyl)cyclohexane, and also diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols H0(CH₂CH₂0)_n-H or polypropylene glycols H0(CH[CH₃]CH₂0)_n-H, where n is an integer and n is ³ 4, polyethylene-polypropylene glycols, where the sequence of the ethylene oxide or propylene oxide units may be blockwise or random, or polytetramethylene glycols, preferably up to a molar mass of 5000 g/mol. The dihydric alcohols may optionally also comprise further functionalities, for example carbonyl, carboxyl, alkoxycarbonyl or sulfonyl functions, for example dimethylolpropionic acid or dimethylolbutyric acid, and the CrC4-alkyl esters thereof, glyceryl monostearate or glyceryl monooleate. The amount of such further dihydric alcohols should, however, generally not exceed 50 mol% based on the amount of all alcohols used (i.e. sum of trifunctional alcohol and difunctional diol). The amount of dihydric alcohols is preferably not more than 30 mol%, more preferably not more than 20 mol%. Most preferably, only the trifunctional alcohols are used.

In a further preferred embodiment, the polyester (a2) is based on a tri- or polycarboxylic acid such as citric acid. Citric acid is particularly preferred. Such polyesters are disclosed e.g. in WO 2012/028496 and WO 2014/016148. According to the invention, citric acid is understood as meaning citric acid anhydrate and also the hydrates of citric acid, such as, for example, citric acid monohydrate.

According to the invention, suitable polyalcohols are alcohols with at least two hydroxyl groups and up to six hydroxyl groups. Preferably, diols or triols or mixtures of different diols and/or triols are contemplated. Suitable polyalcohols are, for example, polyetherols. The polyetherols can be obtained by reaction with ethylene oxide, propylene oxide and/or butylene oxide. In particular, polyetherols based on ethylene oxide and/or propylene oxide are suitable. It is also possible to use mixtures of such polyetherols.

Suitable diols are, for example ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, butane-1, 2- diol, butane-1, 3-diol, butane-1, 4-diol, butane-2, 3-diol, pentane-1, 2-diol, pentane-1, 3-diol, pentane-1, 4-diol, pentane-1, 5-diol, pentane-2, 3-diol, pentane-2, 4-diol, hexane-1, 2-diol, hexane-

1.3-diol, hexane-1, 4-diol, hexane-1, 5-diol, hexane-1, 6-diol, hexane-2, 5-diol, heptane-1, 2-diol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decandiol, 1,10-decandiol,

1.2-dodecandiol, 1,12-dodecandiol, 1,5-hexadiene-3, 4-diol, 1,2- and 1,3-cyclopentanediols, 1,2- , 1,3- and 1 ,4-cyclohexanediols, 1,1-, 1,2-, 1,3- and 1,4-bis(hydroxymethyl)cyclohexanes, 1,1-,

1.2-, 1,3- and 1,4-bis(hydroxyethyl)cyclohexanes, neopentyl glycol, (2)-methyl-2,4-pentanediol,

2.4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2,2,4-tri- methyl-1,3-pentanediol, pinacol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols H0(CH2CH20)_n-H or polypropylene glycols H0(CH[CH₃]CH₂0)_n-H, where n is an integer and n ³ 4, polyethylene polypropylene glycols, where the sequence of the ethylene oxide of the propylene oxide units can be blockwise or random, polytetramethylene glycols, preferably up to a molecular weight up to 5000 g/mol, poly-

1.3-propanediols, preferably with a molecular weight up to 5000 g/mol, polycaprolactones or mixtures of two or more representatives of the above compounds. For example, one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular one diol can be used. Here, one or both hydroxyl groups in the diols specified above can be substituted by SH groups. Diols preferably used are ethylene glycol, 1,2-propane- diol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4- bis(hydroxymethyl)cyclohexane, and diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and polyethylene glycols with an average molecular weight between 200 and 1000 g/mol.

The dihydric polyalcohols can optionally also comprise further functionalities such as, for example, carbonyl, carboxyl, alkoxycarbonyl or sulfonyl, such as, for example, dimethylolpropionic acid or dimethylolbutyric acid, and CrC4-alkyl esters thereof, although the alcohols preferably have no further functionalities.

Preferred diols are ethylene glycol, diethylene glycol and polyethylene glycol with an average molecular weight between 200 and 1000 g/mol.

Suitable triols or higher-functional polyalcohols are, for example, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), trimethylolbutane, trimethylolpentane, 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(hydroxymethyl)amine, tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, pentaerythritol, diglycerol, triglycerol or higher condensation products of glycerol, di(trimethylolpropane), di(pentaerythritol), tris(hydroxymethyl) isocyanurate, tris(hydroxyethyl) isocyanurate (THEIC), tris(hydroxypropyl) isocyanurate and N-[1,3-bis(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]-N,N’- bis(hydroxymethyl)urea.

Preferred triols are trimethylolpropane, trimethylolethane, glycerol, diglycerol and triglycerol, and polyetherols thereof based on ethylene oxide and/or propylene oxide. Also suitable are furthermore sugars or sugar alcohols, such as, for example, glucose, fructose or sucrose, sugar alcohols such as e.g. sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, or inositol.

Also suitable are tri- or higher-functional polyetherols based on tri- or higher-functional alcohols which are obtained by reaction with ethylene oxide, propylene oxide and/or butylene oxide, or mixtures of such reaction products.

It is also possible to use mixtures of at least trifunctional polyalcohols. For example, one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular one at least trifunctional alcohol can be used.

In this connection, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, and diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol with an average molecular weight between 200 and 1000 g/mol, glycerol, diglycerol, triglycerol, trimethylolpropane, trimethylolethane, di(trimethylol- propane), 1,2,4-butanetriol, 1,2,6-hexanetriol, pentaerythritol, sucrose, sorbitol or glucaric acid, and polyetherols thereof based on ethylene oxide and/or propylene oxide, or a mixture thereof are preferred as component B.

Particular preference is given to diethylene glycol or polyethylene glycol with an average molecular weight between 200 and 1000 g/mol, trimethylolpropane, glycerol or diglycerol, triglycerol, and polyetherols thereof based on ethylene oxide and/or propylene oxide, or a mixture thereof.

In addition to the citric acid, further carboxylic acids, in particular saturated dicarboxylic acids, can be condensed in, in which case the fraction of further polycarboxylic acids should be at most 30 mol% compared with the amount of citric acid used. Preferably, the polycarboxylic acids of component C comprise no sulfonate groups.

Suitable saturated dicarboxylic acids are, for example, aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azeleic acid, sebacic acid, undecane-a.oo-dicarboxylic acid, dodecane-a.oo-dicarboxylic acid, cis- and trans-cyclohexane- 1, 2-dicarboxylic acid, cis- and trans-cyclohexane- 1, 3-dicarboxylic acid, cis- and trans-cyclohexane-1, 4-dicarboxylic acid, cis- and trans-cyclopentane- 1,2- dicarboxylic acid, cis- and trans-cyclopentane-1, 3-dicarboxylic acid. The specified saturated dicarboxylic acids can also be substituted with one or more radicals selected from

CrC2o-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, trimethylpentyl, n-nonyl, n-decyl, n- dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, or n-eicosyl,

C2-C2o-alkenyl groups, for example butenyl, hexenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl or eicosenyl, C3-Ci2-cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl and cycloheptyl; alkylene groups such as methylene or ethylidene or

C6-Ci4-aryl groups such as, for example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9- anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.

Exemplary representatives of substituted dicarboxylic acids or derivatives thereof which may be mentioned are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methyl- succinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, 3,3-dimethylglutaric acid, dodecenylsuccinic acid, hexadecenylsuccinic acid and octadecenylsuccinic acid. The dicarboxylic acids can either be used as they are or in the form of derivatives.

Derivatives are preferably understood as meaning the relevant anhydrides in monomeric or else polymeric form, mono- or dialkyl esters, preferably mono- or di-CrC4-alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, as well as mixed esters, preferably mixed esters with different CrC4-alkyl components, particularly preferably mixed methyl ethyl esters.

Among these, preference is given to the anhydrides and the mono- or dialkyl esters, particularly preferably the anhydrides and the mono- or di-CrC4-alkyl esters and very particularly preferably the anhydrides.

Within the context of this specification, CrC4-alkyl means methyl, ethyl, isopropyl, n-propyl, n- butyl, isobutyl, sec-butyl and tert- butyl, preferably methyl, ethyl and n-butyl, particularly preferably methyl and ethyl and very particularly preferably methyl.

Particularly preferably, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, octadecenylsuccinic anhydride, 1,2-, 1,3- or 1 ,4-cyclohexanedicarboxylic acids (hexahydrophthalic acids as cis or trans compounds or mixtures thereof) are used.

Further preferred dicarboxylic acids are glucaric acid and tartaric acid.

The amount of dicarboxylic acid is not more than 30 mol% compared with the amount of citric acid used, preferably not more than 20%, very particularly preferably not more than 15%.

Suitable components D are alkyl- or alkenylcarboxylic acids, such as, for example, long-chain, linear or branched carboxylic acids having 6 to 30 carbon atoms, preferably 8 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the alkyl or alkenyl radical, such as octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, arachic acid, behenic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid or Li, Na, K, Cs, Ca or ammonium salts thereof.

It is also possible to use mixtures.

Preferably, oleic acid, palmitic acid, linoleic acid, stearic acid, lauric acid and ricinoleic acid are used.

The alkyl- or alkenylcarboxylic acids can also be used in the form of their carboxylic acid alkyl esters. Preference is given to using the methyl esters.

Suitable long-chain alcohols are, for example, linear or branched alcohols having 6 to 30 carbon atoms, preferably 8 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as octan-1-ol, decan-1-ol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, behenyl alcohol, 9-hexadecen-1-ol and 9-octadecen-1-ol. Preference is given to using lauryl alcohol and stearyl alcohol.

Exemplary representatives of alkyl- or alkenylamines which may be mentioned are: linear or branched alkylamines having 6 to 30 carbon atoms, preferably 8 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl radical, such as hexylamine, octylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and mixtures thereof.

Suitable long-chain isocyanates are linear or branched isocyanates having 6 to 30 carbon atoms, preferably 8 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl radical, such as octyl isocyanate, dodecyl isocyanate, stearic isocyanate and mixtures thereof.

The molar ratio of (component A + component B) to component D is preferably 10:0.1 to 0.5:0.1, particularly preferably 5:0.1 to 1:0.1.

Preference is given to hyperbranched polyesters which have a weight-average molecular weight in the range from about 500 to 100000, more preferably of 1000 to 50000. In the case of a hyperbranched polyester joined to one polyalkylene oxide group, the molecular weight relates only to the part of the hyperbranched polyester without the polyalkylene oxide group. The determination is usually effected by gel permeation chromatography with a refractometer as the detector. Preference is given to performing the determination as described in the examples.

The polydispersity of the polyesters used in accordance with the invention is generally from 1.2 to 50, preferably from 1.4 to 40, more preferably from 1.5 to 30 and most preferably from 2 to 30. The polydispersity data and the number-average and weight-average molecular weight data M_n and M_w are based here on gel permeation chromatography analyses, using polymethyl methacrylate as the standard and tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol as the eluent. The method is described in Analytiker Taschenbuch [Analyst’s Handbook],

Volume 4, pages 433 to 442, Berlin 1984. The type of terminal groups can be influenced by the ratio of the monomers used. If predominantly OH-terminated polymers are to be obtained, the alcohols should be used in excess. If predominantly COOH-terminated polymers are to be obtained, the carboxylic acids should be used in excess.

The number of free OH groups (hydroxyl number) of the hyperbranched polyester is generally from 10 to 500 mg, preferably from 20 to 450 mg of KOH per gram of polymer and can be determined, for example, by titration to DIN 53240-2.

The number of free COOH groups (acid number) of the hyperbranched polyester is generally from 0 to 400, preferably from 25 to 300, even more preferably 50 to 250 and especially 120 to 250 mg KOH per gram of polymer and can likewise be determined by titration to DIN 53402.

The hyperbranched polyesters used in accordance with the invention generally have at least 4 functional groups. There is in principle no upper limit in the number of functional groups. However, products having too high a number of functional groups frequently have undesired properties, for example poor solubility or a very high viscosity. The hyperbranched polymers used in accordance with the invention therefore generally have not more than 100 functional groups. The hyperbranched polymers preferably have from 6 to 50 and more preferably from 6 to 30 functional groups.

Nitrogen containing hyperbranched polymers (a3)

Additionally preferred are hyperbranched nitrogen-containing polymers a3 from the group of the polyureas, polyurethanes, polyamides, polyesteramides and polyesteramines, whose structure and preparation are described in WO 2006/087227.

Preferred as nitrogen containing hyperbranched polymers (a3) are hyperbranched polyimides. Structure and synthesis of such compounds are disclosed e.g. in WO 2014/032948. Preferred hyperbranched polyimides are based on pyromellitic dianhydride and diphenylmethane diisocyanate.

Further preferred polymers a3 are hyperbranched polyureas, the term “polyurea” in the context of the polymers a3 comprising not just those polymers whose repeat units are joined to one another by urea groups but quite generally polymers obtainable by reacting at least one di- and/or polyisocyanate with at least one compound which has at least one group reactive toward isocyanate groups. These include polymers whose repeat units, as well as urea groups, are also connected by urethane, allophanate, biuret, carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone (oxazolidinone) groups (see, for example, Kunststofftaschenbuch [Plastics Handbook], Saechtling, 26th ed., p. 491ff. , Carl-Hanser-Verlag, Munich 1995). The term “polyureas” comprises especially polymers which have urea and/or urethane groups.

The hyperbranched polymers a3 used in accordance with the invention preferably have, as well as urea and/or urethane groups (or further groups arising from the reaction of isocyanate groups), at least four further functional groups. The proportion of functional groups is preferably 4 to 100, more preferably 4 to 30 and especially 4 to 20. Preference is given to polyureas a3 which have a weight-average molecular weight in the range from about 500 to 100 000, preferably 1000 to 50000.

Their content of urea and/or urethane groups (and, if present, further groups obtained by reaction of an isocyanate group with a group which is reactive toward it and has an active hydrogen atom) is preferably within a range from 0.5 to 10 mol/kg, more preferably 1 to 10 mol/kg, especially 2 to 8 mol/kg.

Useful di- and polyisocyanates include the aliphatic, cycloaliphatic, araliphatic and aromatic di- or polyisocyanates which are known in the prior art and are specified below by way of example. These preferably include 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymeric MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate trimer, 4,4'- methylenebis(cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate where alkyl is Ci-Cio-alkyl, 1,4- diisocyanatocyclohexane or 4-isocyanatomethyl-1 ,8-octamethylene diisocyanate.

Suitable di- or polyisocyanates for forming the polyureas and polyurethanes are more preferably those which have NCO groups of different reactivity. These include 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl-1,6- hexamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3(4)-isocyanatomethyl- 1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, 2,4'-methylene- bis(cyclohexyl) diisocyanate and 4-methylcyclohexane 1,3-diisocyanate (H-TDI).

Additionally suitable for forming the polyureas and polyurethanes are isocyanates whose NCO groups at first have equal reactivity, but in which first addition of a reactant onto one NCO group can induce a decline in reactivity in the second NCO group. The examples thereof are isocyanates whose NCO groups are coupled via a delocalized p electron system, for example 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, toluidine diisocyanate or 2,6-tolylene diisocyanate.

In addition, it is possible to use, for example, oligo- or polyisocyanates which can be prepared from the abovementioned di- or polyisocyanates or mixtures thereof by joining by means of urea, allophanate, urethane, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures.

The compounds having at least two isocyanate-reactive groups used are preferably di-, tri- or tetrafunctional compounds whose functional groups have a different reactivity toward NCO groups.

For the preparation of polyureas, preference is given to using isocyanate-reactive products which have at least two amino groups in the molecule. These are, for example, ethylenediamine, N-alkylethylenediamine, propylenediamine, N- alkylpropylenediamine, hexamethylenediamine, N-alkylhexamethylenediamine, diaminodicyclohexylmethane, phenylenediamine, isophoronediamine, amine-terminated polyoxyalkylenepolyols (so-called Jeffamines), bis(aminoethyl)amine, bis(aminopropyl)amine, bis(aminohexyl)amine, tris(aminoethyl)amine, tris(aminopropyl)amine, tris(aminohexyl)amine, trisaminohexane, 4-aminomethyl-1 ,8-octamethylenediamine, N'-(3-aminopropyl)-N,N-dimethyl- 1,3-propanediamine, trisaminononane or melamine. In addition, mixtures of the compounds mentioned are also usable.

Preferred compounds for preparing polyurethanes and polyurea-polyurethanes are those having at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group, more preferably having at least one hydroxyl group and at least one amino group, in the molecule, especially aminoalcohols, aminodiols and aminotriols, since the reactivity of the amino group compared to the hydroxyl group in the reaction with isocyanate is significantly higher. Examples of the compounds having at least two isocyanate-reactive groups mentioned are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methyl- ethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2- amino-1 ,3-propanediol, 2-amino-2-methyl-1 ,3-propanediol or tris(hydroxymethyl)aminomethane. In addition, mixtures of the compounds mentioned are also usable.

Hyperbranched polyurethanes and polyureas with chain-extended branches can be obtained, for example, by using, for the polymerization reaction, as well as the AB_X molecules, additionally a diisocyanate and a compound which has two groups reactive with isocyanate groups in a molar ratio of 1:1. These additional AA and BB compounds may also possess further functional groups which, however, must not be reactive toward the A or B groups under the reaction conditions. In this manner, further functionalities can be introduced into the hyperbranched polymer.

Linker (b)

The hyperbranched polymer is joined to the polyalkylene oxide chains (c) by means of a linker, preferably polyisocyanate linker. The linker-reactive group used may be a hydroxyl group at the chain end of the polyalkylene oxide chains (c). Polyalkylene oxide chains (c) have exactly one linker-reactive group at the chain end. Suitable polyisocyanate linkers are polyisocyanates with a functionality based on the isocyanate groups of at least 1.5, particularly 1.5 to 4.5 and especially 1.8 to 3.5, comprising aliphatic, cycloaliphatic and aromatic di- and polyisocyanates, and the isocyanurates, allophanates, uretdiones and biurets of aliphatic, cycloaliphatic and aromatic diisocyanates. The polyisocyanates preferably have an average of 1.8 to 3.5 isocyanate groups per molecule. Examples of suitable polyisocyanates are aromatic diisocyanates such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 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, 2,4’-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-1,3-phenylene diisocyanate, 4- ethoxy-1,3-phenylene diisocyanate, 2,4-dimethylene-1 ,3-phenylene diisocyanate, 5,6-dimethyl- 1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, aliphatic diisocyanates such as ethylene diisocyanate, ethylidene diisocyanate, propylene 1,2-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,4-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, and cycloaliphatic diisocyanates such as isophorone diisocyanate (IPDI), cyclohexylene 1 ,2- diisocyanate, cyclohexylene 1 ,4-diisocyanate and bis(4,4’-isocyanatocyclohexyl)methane. Among the polyisocyanates, preference is given to those whose isocyanate groups differ in terms of reactivity, such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 4’-di- phenylmethane diisocyanate, cis- and trans-isophorone diisocyanate, or mixtures of these compounds. Cycloaliphatic diisocyanates, in particular isophorone diisocyanates are preferred.

Polyalkylene oxide shell (c)

The polyalkylene oxide shell (c) comprises (preferably consists of) c1) one or more polyethylene glycol monomethyl ethers and c2) one or more poly(C2-Cs)alkylene glycol mono-(C8-C22)-alkyl ethers, wherein the weight ratio of components d) : c2) is from 9 : 1 to 1 : 9.

The polyethylene glycol monomethyl ether (d) (MPEGs) generally has a molecular weight of 300 to 2000 g/mol, preferably 750 to 1000 g/mol, as determined by GPC. The average number of repeating units p of the ethylen glyol group is generally from 5 to 50, preferably from 15 to 25.

Suitable examples of polyethylene glycol monomethyl ether (d) are compounds of the formula H₃C-(0-CH₂-CH₂)_S -O- wherein s is a natural number from 1 to 50, preferably from 5 to 50, more preferably from 15 to 25. The open bond at the oxygen atom is the typical position where the molecule is bound to the linking group b).

Suitable MPEGs are known and are commercially available, e.g., as Pluriol^® A 350 E, Pluriol^® A 750 E and Pluriol^® A 1020 E from BASF SE, or Carbowax ^® 350 and 750 from Dow Chemicals.

The polyalkylene glycol monoalkyl ethers (c2) are compounds of the formula

R¹-(0-CH₂-CH₂)_q(0-CH(CH₃)-CH₂)r0- wherein each R¹ is independently linear or branched Cs-0₂₂-alkyl; q is a natural number from 1 to 50; and r is 0 or is a natural number from 1 to 30, with the proviso that 5 £ q + r £ 50.

The open bond at the oxygen atom is the typical position where the molecule is bound to the linking group b).

The compound (c2) generally has a molecular weight of from 300 to 2000. Suitable alkyl polyalkylene glykols (FAPEGs) are known and commercially available, e.g., as Lutensol^® AT 11 , Lutensol^® AT 25, Lutensol^® A7N, Plurafac^® LF 1300, LF 700 and LF 1304 from BASF SE or Genapol^® T200-800 and Genapol^® LA070, 160 from Clariant.

As the fatty alcohols R¹-OH often derive from natural sources it is common to have mixtures, e.g. of Ci₆ and Cis alcohols or C12 and C14 alcohols.

The weight ratio (d) : (c2) is in the range of from 9 : 1 to 1 : 9, preferably 7 : 3 to 1 : 9, more preferably 7 : 3 to 2 : 8, even more preferably 5 : 1 to 1:3, and even more preferred 3 : 1 to 1 : 1.5.

In a preferred form the weight ratio (d) : (c2) is in the range of from 85 : 15 to 15 : 85, preferably 8 : 2 to 2 : 8, more preferred 7 : 3 to 3 : 7.

In another form suitable examples of the weight ratio (d) : (c2) are ranges such as from 9 : 1 to 1 : 9, from 7 : 3 to 1 : 9, from 7 : 3 to 2 : 8, from 5 : 1 to 1:3, from 3 : 1 to 1 : 1.5, from 85 : 15 to 15 : 85, from 8 : 2 to 2 : 8, or from 7 : 3 to 3 : 7.

The molar ratio of (d) to (c2) in mol-% is generally in the range of from 95% : 5% to 5% :95%, preferably 80% : 20% to 25% : 75%, more preferred 75%: 25% to 40% : 60%.

In general 70 to 100 % of the groups (d) and (c2) carry an end group R¹ or methyl, preferably at least 95%.

As component (III) the composition comprises a (Cs-C22)-fatty alcohol polyalkoxylate, preferably (Cio-C22)-fatty alcohol polyalkoxylate, more preferably (Ci2-C2o)-fatty alcohol polyalkoxylate, most preferably (Ci4-C2o)-fatty alcohol polyalkoxylate, in particular (Ci₆-Cis)-fatty alcohol polyalkoxylate.

The fatty alcohol may be linear or branched. The terms polyalkoxylate and polyalkoxylated used herein refer to polyether groups derived from alkylene oxide, in particular C2-C4-alkylene oxide, such as ethylene oxide or propylene oxide. Likewise, the terms polyethoxylate and polyethoxylated used herein refer to polyether groups derived from ethylene oxide. Correspondingly, the terms poly-ethoxy-co-propoxylate and poly-ethoxy-co-propoxylated refer to a polyether radical derived from a mixture of ethylene oxide and propylene oxide. Thus, polyethoxylates have repeating units of the formula [CH2CH2O] while poly-ethoxy-co- propoxylates have repeating units of the formulae [CH2CH2O] and [CH(CH₃)CH₂0]. The number of such repeating units will generally range from 2 to 200, in particular from 3 to 100, especially from 3 to 50.

The compositions can further comprise auxiliaries. Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are preferably water but include organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N- methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam ples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl- polyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The amount of the auxiliaries are, for example, 0,1-1 wt-% bactericides, 5-15 wt-% anti-freezing agents, 0,1-1 wt-% anti-foaming agents, and 0,1-1 wt-% colorants.

According to one specific embodiment, the composition comprises at least one dispersant. The concentrate usually comprises not less than 0.05% by weight of dispersants, preferably not less than 0.1% by weight and in particular not less than 0.5% by weight. The composition can comprise not more than 25% by weight of dispersants, preferably not more than 10% by weight and in particular not more than 5% by weight. The invention further relates to a process for producing the inventive composition by contacting the active ingredient (I) with hyperbranched polymer (II) and (Cs-C22)-fatty alcohol polyalkylene glycol (III). The components can be contacted by commonly known methods, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

The invention furthermore relates to a suspension obtainable, preferably obtained, by mixing water and the suspension concentrate according to the invention. The suspension normally arises spontaneously upon mixing. The mixing ratio of water to concentrate can be in the range of from 1000 to 1 up to 1 to 1 , preferably 200 to 1 up to 3 to 1.

The invention furthermore relates to a method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the concentrate according to the invention or the suspension according to the invention is allowed to act on the respective pests, their environment or on the crop plants to be protected from the respective pests, on the soil and/or on undesired plants and/or on the crop plants and/or their environment. In general, the therapeutic treatment of humans and animals is excluded from the method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants.

The invention further relates to a plant propagation material, specifically seeds, comprising the composition of the invention.

When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the compositions of the invention as premix or, if appropriate, immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

The examples which follow illustrate the invention without imposing any limitation.

Examples

Example 1: Synthesis of hyperbranched polymer C

All percentages are weight-% if not otherwise indicated. The OH numbers were measured to DIN 53240. The acid numbers were measured to DIN EN ISO 21214. GPC was carried out with polymethyl methacrylate as standard.

MPEG1 : methyl polyethylene glycol, mean molar mass of 1000 g/mol, OH number of 50 mg KOH/g.

FAPAG: fatty alcohol polyalkylene glycols

FAPAG1: Ci₆-Cis-fatty alcohol ethoxylated (about 4 EO) and propoxylated (about 14 PO). FAPAG2: Ci₆-Cis-fatty alcohol ethoxylated (about 5 EO) and propoxylated (about 8 PO).

IPDI: Isophorondiisocyanat

Poly-THF: Poly-Tetrahydrofurane, molecular weight of 1000 g/mol

1.1 Synthesis of hyperbranched polyester (HPE)

In a four-necked flask equipped with stirrer, reflux condenser, Dean Stark apparatus and internal thermometer citric acid mono hydrate (77.5 g) was mixed with poly-THF (922.5 g, molar ratio with citric acid mono hydrate 2.5:1). The mixture was melted up at 80 °C, and then titanium(IV) butylate (200 mg) was added. Vacuum was applied, and the mixture was heated to 140°C. Water was removed by distillation, and complete conversion was determined based on the amount of water formed, or by determination of the desired acid number.

2.2 Modification of HPE with IPDI and MPEG1 / FAPAG 1 / FAPAG2 in a weight ratio of (2.5 : 1.5 : 1)

Step 1: MPEG (142.3 g) was melted up at 60 °C in a drying oven and mixed with FAPAG1

(85.4 g) and FAPAG2 (56.9 g) under nitrogen. The three components were homogenized at 50 °C. The heat source was removed and IPDI (58.6 g) was added. The NCO content at the start was determined and the reaction mixture was heated to 45 °C. The reaction was continued until the desired NCO content was reached.

Step 2: The product obtained in step 1 (250.9 g) was charged with the hyperbranched polyester PE (100 g), and the NCO content was determined. The catalyst Zinc neodecanoat (200 mg) was added, and the mixture was heated to 80 °C. The reaction was continued to an NCO content of 0.0 % (100% functionalization).

Content of hyperbranched polymer C: 28.5 % HPE, 12.2 % linker IPDI, 29.6% MPEG, 17.4 % FAPAG1, 12.3% FAPAG2. The obtained polymer has the weight average molecular weight of 6050 (Mw) Daltons and the number average molecular weight of 3600 (Mn) Daltons.

Example 2: Preparation of suspension concentrates

Pesticide A: mefentrifluconazole Pesticide B: azoxystrobin Polymer C: hyperbranched polymer C as described above

Fatty alcohol alkoxylate D: (Ci₆-Cis)-fatty alcohol polyalkylene glycol

AFr1: alkylene glycol (antifreeze),

AFo1: silicone based antifoam,

DS1 : polyalkylene glycol ether (dispersing agent),

DS2: phenolsulfonate - aldehyde - urea condensate (dispersing agent), TH1: polysaccharide (thickener),

AFr1 , AFo1 , DS1 and DS2 were added in to 250 g water and homogenized by mixing for 30 minutes. Then, Pesticide A and Pesticide B were added to the mixture and stirred for additional 15 minutes. Thereafter, the mixtures were bead milled in an Eiger Mini 50 Bead Mill comprising a bead chamber. After milling, the remaining ingredients indicated in Table 1 were added, the mixture was filled up to a total volume of 1.0 I with water and then stirred until homogenous mixture was obtained.

Table 1: Suspension concentrates (all data in g/l)

Example 3: Fungicidal activity

The fungicidal activity was tested in the greenhouse on wheat, which was infected with the fungi Puccinia Recondata/Tritici (PUCCRT). The plants were treated with formulations three days after the inoculation at the use rate of 600 ppm (Pesticide A+B) per ha (200 I water/ha). The percentage of the infected leaf surface areas (7 days after inoculation) are summarized in the Table 2.

Table 2: Fungicidal activity

The data shows that the composition A comprising Polymer C and Fatty alcohol alkoxylate D according to the invention has a higher pesticidal activity compared to the control without polymer and to the composition B comprising only Polymer C.

Example 4: Physicochemical properties

4.1 The dispersion stability was tested according to CIPAC MT 180.

4.2 The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s-¹.

4.3 Particle size distribution

Samples of the composition are dispersed in deionized water and analyzed for particle size using a Malvern Mastersizer 2000 Particle Size Analyzer commercially available from Malvern Instruments, Southborough, MA. The sample is dispersed using a small volume recirculator and operations are performed using a standard operating procedure (SOP) created specifically to include such sample parameters as refractive index, mixing speed, analysis time, and number of measurements. Analysis is based on spherical assumptions and results are reported in terms of a volume-weighted diameter (i.e., < 2 pm show the volume-weighted percentage of particles smaller than and equal to 2 pm and Dv(90) signifies the point in the size distribution, up to and including which, 90% of the total volume of material in the sample is ‘contained’). Results are based on an acquisition range of 0.02 - 2000 pm and on the average of two runs.

Table 3: The physical properties of the formulations:

As seen from Table 3, the formulations A and B are comparable. The composition C has high viscosity which is not suitable for the commercial products. Moreover, the formulation C shows crystal growth when it is stored at high temperatures. Further, it has an inferior dispersion stability and it gets worse over storage. The composition A according to the invention is superior to Composition C in terms of physical storage stability and viscosity. Table 4: Suspension concentrates (all data in g/l)

XY-77 is carbonic acid di-alkyl ester polymer with polyether polyol, alkyl isocyante and glycol ether. It is described in US 9,801 ,372 and differs from the polymer C in that it does not have alkyl end groups. The composition of the invention A1 comprising hyperbranched polymer C in combination with fatty alcohol alkoxylate D was compared to a composition D comprising a hyperbranched polymer HY-77 known from US 9,801 ,372 and fatty alcohol alkoxylate D.

Table 5: The physical properties of the formulations:

As can be seen from Table 5, the particle size distribution and viscosity of the composition D increases over storage at 54°C. Whereas the those remain unchanged in the composition A1.

Claims

Claims:

1. A suspension concentrate comprising

I) a pesticidal active ingredient having the solubility in water of not more than 1 g/l at

25°C,

II) a hyperbranched polymer comprising a. a hyperbranched polycondensate with hydroxyl and/or amino end groups condensed to b. one or more linkers connected to c1) one or more polyethylene glycol monomethyl ethers and c2) one or more poly(C2-Cs)alkylene glycol mono-(C8-C22)-alkyl ethers, wherein the weight ratio of components d) : c2) is from 9 : 1 to 1 : 9;

III) a (Cs-C22)-fatty alcohol alkoxylate.

2. The concentrate according to claim 1, comprising 1 to 40% by weight of component (I).

3. The concentrate according to claim 1 or 2, comprising 5 to 30% by weight of component

(II).

4. The concentrate according to any one of claims 1 to 3, comprising 1 to 15% by weight of component (III).

5. The concentrate according to any one of claims 1 to 4, wherein the hyperbranched polycondensate (a) is a polycarbonate (a1), a polyester (a2), a polyimide (a3), a polyurethane (a4) or a polyurea (a5).

6. The concentrate according to any one of claims 1 to 5, wherein the polycondensate (a) amounts to 5 to 70 wt.-% of the total weight of the hyperbranched polymer.

7. The concentrate according to any one of claims 1 to 6, wherein the linkers (b) are polyisocyanates with a functionality based on the isocyanate groups of 1.5 to 4.5.

8. The concentrate according to any one of claims 1 to 7, wherein the polyethylene glycol monomethyl ether (d) has a molecular weight of 300 to 2000 g/mol.

9. The concentrate according to any one of claims 1 to 8, wherein the polyalkylene glycol monoalkyl ethers (c2) are compounds of the formula

R¹-(0-CH₂-CH₂)q(0-CH(CH₃)-CH₂)r-0- wherein each R¹ is independently linear or branched Cs-C22-alkyl; q is a natural number from 1 to 50; and r is 0 or is a natural number from 1 to 30, with the proviso that 5 £ q + r £ 50.

10. The concentrate according to any one of claims 1 to 9, wherein the pesticide (I) is selected from triazole and/or strobilurine fungicides.

11. The concentrate according to claim 10, wherein the triazole fungicide is selected from azaconazole, bitertanol, bromuconazole , cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 2 (2,4- difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2 pyridyl]propan-2-ol, 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4- (trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2- hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, ipfentrifluconazole, mefentrifluconazole, 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1,2,4-triazol-1- ylmethyl)cyclopentanol.

12. The concentrate according to claims 10 or 11, wherein the strobilurine fungicide is selected from azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, or trifloxystrobin.

13. The concentrate according to any one of claims 1 to 10, wherein the pesticide (I) is selected from mefentrifluconazole and/or azoxystrobine.

14. A suspension obtainable by mixing water and the emulsifiable concentrate as defined in any one of claims 1 to 11.

15. A method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the concentrate according to any one of claims 1 to 11 or the suspension according to claim 12 is allowed to act on the respective pests, their environment or on the crop plants to be protected from the respective pests, on the soil and/or on undesired plants and/or on the crop plants and/or their environment.