EP2180785A2 - Utilisation d'homo- et de copolymeres pour la stabilisation de formulations de substances actives - Google Patents

Utilisation d'homo- et de copolymeres pour la stabilisation de formulations de substances actives

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Publication number
EP2180785A2
EP2180785A2 EP08774789A EP08774789A EP2180785A2 EP 2180785 A2 EP2180785 A2 EP 2180785A2 EP 08774789 A EP08774789 A EP 08774789A EP 08774789 A EP08774789 A EP 08774789A EP 2180785 A2 EP2180785 A2 EP 2180785A2
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EP
European Patent Office
Prior art keywords
active ingredient
weight
monomers
active
homo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP08774789A
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German (de)
English (en)
Inventor
Murat Mertoglu
Holger TÜRK
Chee Chin Liew
Ulrike Troppmann
Reiner Weiler
Günter OETTER
Cedric Dieleman
Winfried Mayer
Lars Vicum
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BASF SE
Original Assignee
BASF SE
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Publication date
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Priority to EP08774789A priority Critical patent/EP2180785A2/fr
Publication of EP2180785A2 publication Critical patent/EP2180785A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to the use of certain homo- or copolymers P for the stabilization of organic active ingredients in aqueous compositions or formulations containing surface-active substances.
  • Active ingredients d. H. Substances which, even at low concentrations, can already have a physiological effect, in particular active ingredients for crop protection, are frequently formulated or used in the form of aqueous active substance compositions.
  • the active ingredients used for pest control or growth promotion d. H. Insecticides, fungicides, herbicides and growth regulators, often formulated and sold as aqueous concentrates.
  • these formulations but also non-aqueous liquid formulations such as emulsion concentrates and water-dispersible powders or granules before use diluted by adding a large amount of water to the desired application concentration (so-called spray mixture).
  • aqueous active substance compositions have proven useful.
  • a fundamental problem in the formulation and application of organic active ingredients in an aqueous medium is the generally low water solubility of the active compounds, which is frequently less than 10 g / l, in particular less than 1 g / l and especially not more than 0.1 g / l at 23 0 C is.
  • Aqueous compositions of these agents are therefore heterogeneous systems wherein the active ingredient is present as an emulsified or dispersed phase in a continuous aqueous phase.
  • active ingredient formulations usually contain surface-active substances such as emulsifiers, wetting agents and / or dispersants.
  • adjuvants are also surface-active substances.
  • these adjuvants bring about a more uniform distribution of the organic active ingredient in the aqueous phase, be it in the aqueous phase of a concentrated formulation or in the spray mixture.
  • the better distribution of the drug is often due to a solubilizing effect of the adjuvant.
  • adjuvants are frequently also added in order to achieve a better penetration of the active ingredient into the treated skin To reach plant tissue. This is particularly important in systemically acting crop protection agents of importance.
  • aqueous formulations of active substances are often unstable and tend to agglomerate or crystallize the active ingredient particles and, as a consequence, to separate the active ingredient distributed in the aqueous phase, for example by creaming or sedimentation.
  • These problems are particularly pronounced if the formulation is stored for a long time at elevated temperature and / or at strongly changing temperatures or even near freezing.
  • This problem is particularly pronounced when the drug tends to crystallize, eg. B. in drugs with a low melting point (below 80 0 C) and / or in active ingredients which have a limited solubility in the aqueous phase and / or the surfactant. Crystallization problems often occur when the formulation contains larger amounts of surface-active substances, in particular those with polyalkylene ether groups, since these can increase the solubility of the active ingredient in the aqueous phase and promote crystallization or agglomeration processes.
  • Another problem with the formulation of drugs with limited or extremely low water solubility is that dilution of the drug formulations to the desired use concentration may result in deposition of the drug. This not only results in a loss of efficiency of the active substances, but in the case of spray mixtures there is also the risk of blockage for filter and nozzle systems. This problem is particularly pronounced in the case of aqueous active ingredient formulations with a greater content of surface-active substances and / or organic co-solvents and emulsifiable concentrates.
  • SC formulations suspension concentrates
  • ME formulations microemulsion concentrates
  • solvent-containing formulations such as emulsifiable concentrates (EC formulations) or solutions the active ingredients in water-miscible solvents (DC formulations) a problem.
  • US Pat. No. 5,205,225 describes formulation of azole fungicides which contain, in addition to conventional surface-active substances, dimethylamides of aliphatic carboxylic acids.
  • the dimethylamides of the aliphatic carboxylic acids serve to reduce the deposition of the azole fungicide upon dilution of the formulation.
  • WO 03/00716 describes liquid formulations of azole fungicides which contain polyvinyl alcohol as crystallization inhibitor.
  • WO 03/055944 describes the use of hydrophobically modified polymers containing sulfonic acid groups as a crystallization inhibitor in formulations containing crop protection active ingredients.
  • the stabilizing effect of the crystallization inhibitors known from the prior art is often unsatisfactory for many drugs with low water solubility, especially when the formulation of the drug contains larger amounts of surfactants. This problem is particularly pronounced when the surface-active substances contained in the formulation cause a solubilization of the active ingredient in the aqueous phase, for.
  • the object of the present invention is thus to provide substances which bring about a stabilization of active substances with low water solubility in an aqueous phase if the aqueous phase contains one or more surface-active substances, in particular those having a solubilizing effect for the active substance.
  • these stabilizing substances should make it possible to stabilize active substances which tend to crystallize, especially azole fungicides, fungicidal carboxamides, in particular fungicidal carboxanilides, strobilurins and mixtures thereof.
  • homo- and copolymers P consisting of monoethylenically unsaturated monomers M, comprising:
  • the monomers M1 and M2 constitute at least 70 wt .-% of the monomers M.
  • the present invention relates to the use of homopolymers and copolymers P composed of monoethylenically unsaturated monomers M, comprising:
  • the monomers M1 and M2 constitute at least 70% by weight, in particular at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight and especially at least 99% by weight of the monomers M; for stabilizing poorly soluble in water organic active ingredients in aqueous compositions containing surface-active substances.
  • the homopolymers and copolymers P stabilize the active substance particles distributed in the aqueous phase against particle enlargement, in particular a particle enlargement caused by crystallization in the case of agents prone to crystallization. In this way, they effectively counteract the settling or deposition of the active ingredient. Even at higher storage temperatures occurs in aqueous drug compositions containing in addition to the / in water sparingly soluble active ingredient (s) at least one of the polymers P according to the invention, a particle enlargement of the suspended drug particles not or only very delayed or to a much lesser extent.
  • the stabilizing effect is not based on aqueous formulations of the active ingredient, which contain the active ingredient in concentrated form, d. H. suspension diluents, but also occurs in dilute drug formulations such as dilute aqueous formulations such as SC or ME formulations, or even dilute non-aqueous liquid formulations such as EC and DC formulations or solid formulations such as water-dispersible powders (WP formulations) or water-dispersible granules (WG formulations) can be obtained.
  • WP formulations water-dispersible powders
  • WG formulations water-dispersible granules
  • the stabilizing effect of homopolymers and copolymers P also occurs when a conventional formulation, which does not necessarily contain a homo- and copolymer P, diluted with water with the addition of a homo- or copolymer P.
  • Another advantage of the invention is that in the preparation of aqueous formulations of poorly water-soluble active ingredients by a grinding process, the energy and time can be reduced by adding the homo- or copolymers P can, as usually the desired fineness of the active ingredient in the formulation with fewer milling times or shorter milling time can be achieved compared to the preparation without the addition of at least one homo- or copolymer P.
  • the invention therefore relates to formulations containing a) at least one homo- or copolymer P as described here or in the claims, b) at least one surface-active substance, c) at least one sparingly soluble in water organic active substance, and d) optionally water.
  • the invention also relates to aqueous active substance compositions comprising:
  • An organic active compound which is poorly soluble in water is understood as meaning an organic compound or a mixture of various organic compounds which, in water at 23 ° C., has a solubility of generally not more than 10 g / l, often not more than 2 g / l. in particular not more than 1 g / l and especially not more than 0.1 g / l.
  • Active substances in the context of the present invention are chemically defined substances which in an organism, usually even at low application rates, specifically produce an effect or a reaction.
  • Active substances in the context of this invention are, in particular, organic compounds having a defined molecular composition (empirical formula) and a molecular weight which is typically not more than 2000 daltons, in particular not more than 1000 daltons and preferably in the range from 100 to 1000 daltons and especially Range of 150 to 500 daltons.
  • a composition according to the invention is understood as meaning both nonaqueous and aqueous active substance concentrates and aqueous administration forms (eg spray liquors) of the at least one organic active substance.
  • Concentrates are to be understood as meaning those compositions which have at least 1 g / l, in particular at least 10 g / l, z. B. 10 to 800 g / l, often 10 to 600 g / l or 10 to 500 g / l, especially 20 to 400 g / l, of at least one organic active ingredient.
  • dilute forms of administration are understood as meaning aqueous compositions which are obtained by diluting an aqueous or nonaqueous active substance concentrate with water and which accordingly have an active substance concentration of generally less than 10 g / l, eg. From 0.0001 to ⁇ 10 g / l, often less than 5 g / l or less than 1 g / l, e.g. From 0.0005 to ⁇ 5 g / l or from 0.001 to ⁇ 1 g / l.
  • the polymers used according to the invention are homo- or copolymers P, the acrylic acid or methacrylic acid or a mixture of these acids (hereinafter monomers M1) in an amount of at least 10 wt .-%, in particular at least 20 wt .-%, preferably at least 30 wt .-%, more preferably at least 40 wt .-% and especially at least 50 wt .-% copolymerized contain.
  • the proportion of the monomers M1, based on the total amount of the homo- or copolymer constituent monomers M can be up to 100 wt .-%. In this case, they are homopolymers or copolymers of the monomers M1 which consist exclusively of the monomers M1.
  • copolymers are used which, in addition to the abovementioned monomers M1, comprise at least 1 further monomer M2 in copolymerized form.
  • the proportion of monomers M2 is 1 to 90% by weight, in particular 2 to 80% by weight, particularly preferably 5 to 70% by weight, particularly preferably 10 to 60% by weight and especially 10 to 50 % By weight, based on the total weight of the monomers M.
  • the proportion of the copolymerized monomers M1 in these copolymers is in the range from 10 to 99% by weight, in particular from 20 to 98% by weight, particularly preferably from 30 to 95 wt .-%, particularly preferably 40 to 90 wt .-% and especially 50 to 90 wt .-%.
  • the total amount of the monomers M1 and M2 makes according to the invention at least 70 wt .-%, often at least 80 wt .-%, preferably at least 90 wt .-%, in particular at least 95 wt .-%, particularly preferably at least 99 wt .-% and especially 100 wt .-% of the monoethylenically unsaturated monomers M, which constitute the homo- or copolymer P, from.
  • the homopolymers and copolymers P according to the invention preferably comprise less than 5% by weight, based on the total amount of the monomers M and in particular no or less than 0.5% by weight of monomers with phosphonic acid groups or sulfonic acid groups in copolymerized form.
  • methacrylic acid is preferred.
  • monomers M2 preference is given to those monomers which have at least limited water solubility, generally a water solubility of at least 1 g / l, frequently at least 5 g / l, preferably at least 10 g / l and especially at least 20 g / l at 25 ° C C have.
  • monomers M2 are examples of such monomers M2 are
  • - C 1 -C 4 -alkyl acrylates and methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate and n-butyl acrylate;
  • Hydroxyalkyl acrylates and methacrylates in particular hydroxy-C 2 -C 3 -alkyl acrylates and methacrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate; Amides, N-Ci-C4-alkylamides and N, N-di-Ci-C4-alkylamides of acrylic acid or the
  • Methacrylic acid such as acrylamide, methacrylamide, N, N-dimethylacrylamide or
  • Vinyl ethers in particular vinyl-C 1 -C 4 -alkyl ethers such as vinyl methyl ether, vinyl ethyl ether and the like; and N-vinyl lactams, preferably those having 3 to 5 carbon atoms in Lactamring such as N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam.
  • the monomers M2 may also include minor amounts of monomers having a low water solubility of generally below 5 g / l, in particular below 1 g / l at 25 0 C). These low water solubility monomers are preferably used in combination with monomers M2 which have limited water solubility (at least 1 g / l, often at least 5 g / l, preferably at least 10 g / l and especially at least 20 g / l at 25 ° C.), used to prepare the polymers P. The proportion of monomers having low solubility in water will generally not exceed 20% by weight, based on the total amount of monomers M. Examples of monomers with low water solubility are:
  • C 5 -C 20 -alkyl acrylates and methacrylates such as n-hexyl acrylate, n-octyl acrylate, n-decyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, stearyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate,
  • Vinylaromatic monomers such as styrene and vinyltoluene
  • Vinyl esters of aliphatic carboxylic acids preferably having 4 to 20 C atoms, such as vinyl laurate and vinyl stearate;
  • Vinyl ethers in particular vinyl C 4 -C 20 -alkyl ethers such as vinylhexyl ether, vinyldecyl ether, vinyl octadecyl ether and the like; and olefins having 2 to 20 C atoms such as ethene, propene, 1-butene, isobutene, n-hexene, diisobutene, trimers and tetramers of butene or isobutene.
  • vinyl C 4 -C 20 -alkyl ethers such as vinylhexyl ether, vinyldecyl ether, vinyl octadecyl ether and the like
  • olefins having 2 to 20 C atoms such as ethene, propene, 1-butene, isobutene, n-hexene, diisobutene, trimers and tetramers of butene or isobutene.
  • the monomers M2 are selected from monomers having a limited water solubility of generally not more than 60 g / l, e.g. B. 1 to 60 g / l, in particular 10 to 60 g / l at 25 0 C.
  • N-C 1 -C 3 -alkylamides of acrylic acid or of methacrylic acid N, N-di-C 1 -C 3 -alkylamides of acrylic acid or of methacrylic acid, vinyl esters of aliphatic C 1 -C 3 -carboxylic acids, C 1 -C 3 -alkyl vinyl ethers and C 4 -alkyl acrylates and C 1 -C 4 -alkyl methacrylates, preference being given to C 1 -C 4 -alkyl acrylates and C 1 -C 4 -alkyl methacrylates.
  • the monomers M2 are selected from methyl acrylate and methyl methacrylate and mixtures thereof and mixtures thereof with up to 20% by weight of monomers having low water solubility.
  • the monomers M2 are selected from monomers having a substantial or complete water solubility of generally at least 60 g / l, in particular at least 80 g / l at 25 ° C. These include, in particular, the abovementioned hydroxyalkyl acrylates, hydroxyalkyl methacrylates and N-vinyllactams.
  • the polymer P is composed exclusively of acrylic acid, methacrylic acid or a mixture of these acids.
  • the polymer P is composed of monomers M comprising methacrylic acid as monomer M1 and methyl acrylate, methyl methacrylate or mixtures thereof as monomer M2.
  • the polymer P is composed exclusively of methacrylic acid and methyl acrylate, methyl methacrylate or mixtures thereof.
  • the weight ratio of monomer M1 to monomer M2 is in the range of 50: 1 to 1: 5, more preferably in the range of 20: 1 to 1: 1, and especially in the range of 10: 1 to 2: 1 ,
  • homo- or copolymer Ps which have a weight-average molecular weight in the range from 500 to 200,000 daltons, in particular from 1000 to 70,000 daltons and particularly preferably from 2,000 to 30,000 daltons.
  • the molecular weight can be determined in a manner known per se by light scattering or gel permeation chromatography according to methods known per se.
  • An indirect measure of the molecular weight is the so-called K value according to Fikentscher (H.
  • the K value determined as 0.1% by weight .-% solution of the homo- or copolymer P in 0.1 M aqueous sodium chloride solution or in a mixture of 0.1 M aqueous sodium chloride solution and methanol, is usually in the range of 5 to 100, often in Range from 7 to 80, especially in the range of 10 to 50 and especially in the range of 12 to 40.
  • the homopolymers and copolymers P are preferably used in acidic or, in particular, partially neutralized form.
  • the degree of neutralization of the homopolymers and copolymers P ie the proportion of neutralized carboxyl groups which result from the polymerized acrylic acid or methacrylic acid not above 90%, in particular not above 80%, preferably not above 70%, especially not above 50%.
  • the degree of neutralization is> 0 to 70%, preferably> 0 to 50% and particularly preferably> 0 to 30%, z.
  • B. 1 to 70% preferably 1 to 50%, in particular 1 to 30%, especially between see 0 and 30%, z. From 1 to 29%.
  • bases which are suitable for neutralizing carboxyl groups.
  • suitable bases are alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, ammonia and organic amines.
  • Preferred bases are alkali metal hydroxides and alkali metal carbonates, especially sodium hydroxide or potassium hydroxide. It is also possible, in the preparation of the homo- and copolymers P, to start from neutralized or partially neutralized acrylic acid or methacrylic acid.
  • the homo- and copolymers P can be prepared by conventional methods by radical polymerization of the monomers M.
  • the polymerization can be carried out by free radical polymerization or by controlled radical polymerization.
  • the polymerization can be carried out using one or more initiators and as a solution polymerization, as an emulsion polymerization, as a suspension polymerization or as a precipitation polymerization or in bulk.
  • the polymerization can be carried out as a batch reaction, in a semicontinuous or continuous mode.
  • the reaction times are generally in the range between 1 and 12 hours.
  • the temperature range in which the reactions can be carried out generally ranges from 20 to 200 0 C, preferably from 40 to 120 0 C.
  • the polymerization pressure is of minor importance and can be in the range of atmospheric pressure or slight negative pressure, for. B.> 800 mbar or at overpressure, z. B. to 10 bar, with higher or lower pressures can also be applied.
  • initiators for the radical polymerization customary radical-forming substances are used.
  • initiators are selected from the groups of azo compounds, peroxide compounds and hydroperoxide compounds.
  • the peroxide compounds include, for example, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxyisobutyrate, caproyl peroxide.
  • the hydroperoxides also include organic peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide and the like.
  • the azo compounds include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 1 , 1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyramidine).
  • AIBN azobisisobutyronitrile
  • the initiator is used in an amount of 0.02 to 5 wt .-% and in particular 0.05 to 3 wt .-%, based on the amount of the monomers M, wherein it is also possible to use larger amounts, for. B. up to 30 wt .-%, for example in the case of hydrogen peroxide.
  • the optimum amount of initiator naturally depends on the initiator system used and can be determined by the person skilled in the art in routine experiments.
  • the initiator may be partially or completely charged in the reaction vessel.
  • the main amount of the initiator in particular at least 80%, z. B. 80 to 100% of the initiator in the course of the polymerization in the polymerization reactor.
  • the molecular weight of the homopolymers and copolymers P by adding regulators in a small amount, for. B. 0.01 to 5 wt .-%, based on the polymerizing monomers M, can be adjusted.
  • a regulator in particular organic thio compounds z.
  • mercapto alcohols such as mercaptoethanol, mercaptocarboxylic acids such as thioglycolic acid, mercaptopropionic acid, alkyl mercaptans such as dodecyl mercaptan, also allyl alcohols and aldehydes into consideration.
  • the preparation of the homopolymers and copolymers P takes place by free-radical solution polymerization in an organic solvent or solvent mixture.
  • organic solvents are alcohols, such as. For example, methanol, ethanol, n-propanol and isopropanol, dipolar aprotic solvents, eg. B.
  • N-alkyl lactams such as N-methylpyrrolidone (NMP), N-ethylpyrrolidone, furthermore dimethyl sulfoxide (DMSO), N, N-dialkylamides of aliphatic carboxylic acids such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, furthermore aromatic aliphatic and cycloaliphatic hydrocarbons which may be halogenated, such as hexane, chlorobenzene, toluene or benzene and mixtures thereof.
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • N-dialkylamides of aliphatic carboxylic acids such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide
  • aromatic aliphatic and cycloaliphatic hydrocarbons which may be halogenated, such as hexane, chlorobenzene, tol
  • Preferred solvents are isopropanol, methanol, toluene, DMF, NMP, DMSO and hexane, particularly preferred is isopropanol.
  • the preparation of the homopolymers and copolymers P in a mixture of the solvents and solvent mixtures described above can be carried out with water.
  • the water content of these mixtures is preferably less than 50% by volume and in particular less than 10% by volume.
  • the actual polymerization, a post-polymerization, z. B. by adding a red-ox initiator system connect.
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is z. B. to the above-mentioned peroxide.
  • the reduction components are, for. B. to alkali metal salts of sulfurous acid, such as.
  • the red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual Red Ox initiator systems are z.
  • the individual components eg. As the reduction component, can also Be mixtures, for. B. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the homo- and copolymers P used according to the invention are usually used in an amount of at least 1% by weight, preferably at least 5% by weight and in particular at least 10% by weight, based on the active substance (s) to be stabilized ) used.
  • the homo- and copolymers P are preferably used in an amount of from 5 to 2000% by weight, frequently from 10 to 1000% by weight, preferably from 10 to 500% by weight or from 10 to 100% by weight, in particular in one Amount of 10 to 60 wt .-%, based on the or the active ingredient (s).
  • the concentration of the homopolymers or copolymers P is typically in the range from 0.01 to 15% by weight, in particular in the range from 0.1 to 10% by weight and especially in the range from 0.5 to 6 Wt .-%, based on the total weight of the aqueous composition.
  • the homo- or copolymer P is generally employed in an amount of 0.05 to 20 parts by weight, preferably in an amount of 0.1 to 10 parts by weight, based on 1 part by weight of the active ingredient.
  • the active ingredient preparations obtainable by dilution with water contain the polymer P in an amount of 0.01 to
  • the homo- and copolymers P are used together with at least one surface-active substance.
  • surface-active substances such as nonionic and anionic emulsifiers and protective colloids, as well as further solubilizing polymers known to be used for the stabilization of active substances in the aqueous phase.
  • Emulsifiers / surfactants and protective colloids are known to the person skilled in the art, eg. See, for example, H. Mollet et al., Formulation Technology, pp. 27-24 and pp. 65-73, Wiley-VCH, Weinheim 2001, and R. Heusch, Emulsions in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. On CD -Rom, Wiley-VCH 1998.
  • nonionic, anionic, cationic or zwitterionic emulsifiers examples of conventional surface-active substances are the nonionic, anionic, cationic or zwitterionic emulsifiers, wetting agents or dispersants specified below, for example.
  • aliphatic Cs-Cso alcohols which may be alkoxylated, for. B. with 1 to 60 Alky- lenoxidiseren, preferably 1 to 60 EO and / or 1 to 30 PO and / or 1 to
  • EO stands for one of ethylene oxide
  • PO for one of propylene oxide
  • BO for a butylene oxide derived repeat development unit.
  • the terminal hydroxy groups of these compounds may be end-capped by an alkyl, cycloalkyl or acyl radical containing 1 to 24, especially 1 to 4, carbon atoms.
  • Examples of such compounds are: Genapol ® C, L, O, T, UD, UDD, X-products of Clariant, Plurafac ® - and Lu Tensol ® A, AT, ON, TO products of BASF SE, Marlipal ® 24 and 013 products from Condea, Dehypon ® products from Henkel, Ethylan ® products from Akzo Nobel such as Ethylan CD 120;
  • Copolymers consisting of EO, PO and / or BO units, in particular EO / PO block copolymers such as the Pluronic ® products from BASF SE and
  • Fatty acid such as the Comperlan® ® products from Henkel or on the ® - products from Rhodia;
  • Alkylene oxide adducts of alkyne diols such as the Surfynol ® products from Air Products.
  • Sugar derivatives such as amino and amido sugars from Clariant.
  • Alkylene oxide adducts based polyol such as polyglycol ® products from Clariant;
  • surfactant polyglycerides and their derivatives from Clariant b8) surfactant polyglycerides and their derivatives from Clariant; b9) sugar surfactants, e.g. B. alkoxylated sorbitan fatty acid esters, alkyl polyglycosides and their alkoxylated derivatives;
  • Per- or polyfluorinated surface-active compounds such as Fluowet ® products from Clariant, the Bayowet ® products from Bayer, the Zo nyl ® - products from DuPont and products of this type from Daikin and Asahi Glass;
  • neutral surfactant polyvinyl compounds such as modified polyvinylpyrrolidone such as the Luviskol ® products from BASF and the Agrimer ® products from ISP or the derivatized polyvinyl acetates such as the Mowilith ® products from Clariant or the butyrates such as the Lutonal ® products from BASF, the Vinnapas ® - and the
  • Phosphoric acid mono- or diesters of the substances described under b1), and their inorganic (eg., NH 4 +, alkali and alkaline earth metal salts) and organic salts (for. Example based on amine or alkanolamine) such as Genapol ® LRO, Sandopa n ® - products, Hostaphat / Hordaphos ® products from Clariant;
  • anionic derivatives of the products described under b17) in the form of ether carboxylates, sulfonates, sulfates ( sulfuric monoesters) and phosphates (Phosphorklamono- or diesters) of the substances described under b17), for example, the acidic phosphoric acid esters with 2 to 10 moles of ethylene oxide ethoxylated Ci-Ci6-alkylphenol, z.
  • benzenesulfonates such as alkyl or arylbenzenesulfonates, e.g. B. acidic and neutralized with suitable bases (poly) alkyl and (poly) arylbenzenesulfonates, for example having 1 to 12 carbon atoms per alkyl radical or with up to 3 styrene units in the polyaryl, preferably (linear) dodecylbenzenesulfonic acid and its oil-soluble salts such as the calcium salt or the isopropylammonium salt of dodecylbenzenesulfonic acid and acidic (linear) dodecylbenzenesulfonate, commercially for example in the form of the Marlon® products (Hüls);
  • lignin sulfonates such as sodium, calcium or ammonium lignosulfonates as UFO Xane ® 3A, Borresperse AM ® 320 or ® Borresperse NA;
  • arylsulfonic acids such as phenolsulfonic acid or naphthalenesulfonic acid with formaldehyde and optionally urea, in particular their salts and especially the alkali metal salts and calcium salts, eg. B. the Ta mol ® - and Wettol ® - BASF SE as Wettol ® brands D1;
  • alkanesulfonates such as Netzer IS ®, ® Hoe S1728, Hostapur ® OS, Hostapur ® SAS from Clariant;
  • alkyleneoxy units or alkylene ether units preference is given to ethyleneoxy, propyleneoxy and butyleneoxy units, in particular ethyleneoxy units and mixtures of ethyleneoxy units and propyleneoxy units.
  • Alkoxylated means that the surface-active substance has a polyalkylene ether group, in particular a poly-C 2 -C 4 -alkylene ether group, especially a poly-C 2 -C 3 -alkylene ether group.
  • the number of alkyleneoxy units in the polyalkyleneoxy or polyalkylene ether groups in the substances of groups b1), b3), b4), b5), b7), b9), b10), b11), b17), b18) and b19) typically range from 2 to 150, especially 2 to 100, especially 3 to 60 (number average).
  • Preferred conventional nonionic surface-active substances are the substances mentioned under b1), in particular ethoxylated and / or propoxylated C8-C24 alkanols, the substances mentioned in group b2), in particular EO7PO block copolymers, the substances mentioned in group b3), in particular alkoxy vegetable oils, the substances mentioned in group b4), the products mentioned in group b9), the substances mentioned in group b10) and the substances mentioned in group b17), in particular ethoxylated and / or propoxylated alkylphenols.
  • Preferred conventional anionic surface-active substances are the substances mentioned under b18), b19), b22) and b23), in particular the substances mentioned under b22) and b23).
  • Solubilizing polymers in the context of the invention are those polymers which lead to an extremely fine, ie nanodisperse, distribution of the active ingredient in the aqueous phase so that the apparent particle size of the active ingredient particles is well below 1000 nm, typically not more than 500 nm, often not more than 400 nm, in particular not more than 300 nm, more preferably not more than 250 nm, more preferably not more than 200 nm, z. B.
  • the aggregates may also become so small that they are no longer in the form of detectable, discrete particles (particle size ⁇ 20 nm, ⁇ 10 nm or ⁇ 5 nm) ,
  • the particle sizes given here are volume-average particle sizes, as can be determined by light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D.
  • the aqueous composition of the active substance to be stabilized contains at least one surface-active substance which has one or more poly-C 2 -C 4 -alkylene ether groups.
  • poly-C 2 -C 4 -alkylene ether groups include in particular nonionic emulsifiers which have one or more P0IV-C 2 -C 4 -alkylene ether groups, and also solubilizing polymers which have one or more poly-C 2 -C 4 -alkylene ether groups.
  • the number of C 2 -C 4 -alkyleneoxy units in the poly-C 2 -C 4 -alkylene ether groups in the substances of groups b1), b3), M), b5), b7), b9), b10), b11), b17) , b18) and b19) are typically in the range of 2 to 150, especially 2 to 100, especially 3 to 60 (number average).
  • preference is given to those substances in which the alkyleneoxy units of the P0IV-C 2 -C 4 -alkylene ether groups are selected from 1,2-ethyleneoxy and 1,2-propyleneoxy units and mixtures thereof.
  • Suitable solubilizing polymers are, in particular, block copolymers which have one or more poly-C 2 -C 4 -alkylene ether groups and at least one polymer chain composed of monoethylenically unsaturated monomers.
  • the blocks can be directly, d. H. via a chemical bond, or via spacer, d. H. be linked together via a polyvalent organic radical.
  • Polyvalent means here that the organic residue on average at least 1, 5, in particular at least two binding sites, for. B. 1, 5 to 6 or 2 to 4 binding sites.
  • the block copolymers are those in which at least one poly-C 2 -C 4 -alkylene ether group has at least one from monoethyne groups via a spacer which has urethane groups. lenisch unsaturated monomers constructed polymer chain are linked.
  • Such block copolymers are known, for example, from WO 2005/121201 and WO 2006/084680, the disclosure of which is hereby incorporated by reference.
  • polymer chain P1 the polymer chain composed of monoethylenically unsaturated monomers typically has a number average molecular weight in the range from 500 to 20,000 daltons and in particular in the range from 1500 to 15,000 daltons.
  • the poly-C 2 -C 4 -alkylene ether group in the following polymer chain P2 generally has a number-average molecular weight, determined by GPC by customary methods, in the range from 500 to 20,000 daltons and in particular in the range from 800 to 15,000 Dalton on.
  • the total proportion of the polymer chain P1 on the block copolymer is preferably 9 to 90 and in particular 20 to 68 wt .-% of the total weight of polymer chain P1, polymer chain P2 and optionally spacer.
  • the total proportion of the polyethers P2 on the block copolymer is preferably 9 to 90 and in particular 30 to 78 wt .-% of the total weight of polymer chain P1, polymer chain P2 and optionally spacer.
  • the total proportion of the spacer in the block copolymer will generally not exceed 20% by weight, based on the total weight of the block copolymer, and, if a spacer is present, is frequently from 1 to 20 and especially from 2 to 15% by weight of the total weight of Polymer chain P1, polymer chain P2 and spacer.
  • the weight ratio of polymer chain P1 to poly-C2-C4-alkylene ether group P2 in the block copolymers is preferably in the range from 1:10 to 10: 1 and in particular in the range from 1: 5 to 5: 1.
  • polymer chain P1 ( '' the monomers M) are, in particular neutral, monoethylenically unsaturated monomers Ma with a limited solubility in water of usually not more than 60 g / l at 25 0 C (hydrophobic Monomers) and monomers Mb with increased water solubility.
  • the monomers M ' preferably comprise
  • the data in% by weight being based on the total amount of the monomers M '.
  • esters of acrylic acid or of methacrylic acid with 2-phenoxyethanol such as 2-phenoxyethyl acrylate.
  • N- (C 2 -C 10 -alkyl) amides of monoethylenically unsaturated C 3 -C 8 -carboxylic acids especially those of acrylic acid and of methacrylic acid
  • N- (C 1 -C 2 -alkyl) -N- (C 2 -C 10 -alkyl) amides monoethylenically unsaturated Cs-Cs carboxylic acids especially of acrylic acid and methacrylic acid, z.
  • vinylaromatic monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, etc.
  • olefins having 2 to 20 C atoms, preferably ⁇ -olefins having 3 to 10 C atoms such as propene, 1-butene, 1-pentene, 1 Hexanes, 1-octene, diisobutene and 1-decene
  • vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl lactate, vinyl nonanoate, vinyl decanoate, vinyl laurate and vinyl stearate
  • halogenated olefins such as vinyl chloride
  • di-Ci-C2- Alkyl esters of ethylenically unsaturated dicarboxylic acids having preferably 4 to 8 carbon atoms, for.
  • Di-C 1 -C 20 -alkyl esters of fumaric acid and maleic acid such as dimethyl fumarate, dimethyl maleate, dibutyl fumarate and dibutyl maleate
  • the monomers Ma comprise at least 50% by weight, in particular at least 70% by weight, based on the total amount of the monomers Ma, at least a selected from Ci-C4-alkyl acrylates, Ci-C4-alkyl methacrylates and styrene monomers include, and among these particularly preferably methyl methacrylate, tert-butyl methacrylate, styrene and mixtures thereof.
  • Preferred monomers Ma are also mixtures of the abovementioned monomers Ma, which predominantly, in particular at least 60 wt .-% and particularly preferably 70 wt .-%, z. B. 60 to 99 wt .-% or 70 to 99 wt .-%, based on the total amount of the monomers Ma, at least one of Ci-C4-alkyl acrylates, Ci-C 4 -AlkVl- methacrylates and styrene selected first monomers Ma and at least one of them different monomer Ma, z.
  • the monoethylenically unsaturated monomers Mb can be basic or cationic, acidic or anionic or nonionic, ie. H. be electrically neutral.
  • Examples of neutral monomers Mb include
  • Cs-Cs monocarboxylic acids such as acrylamide, methacrylamide, N- (methoxymethyl) (meth) acrylamide, N- (ethoxymethyl) (meth) acrylamide,
  • N-vinylamides of aliphatic, cycloaliphatic or aromatic carboxylic acids in particular N-vinylamides of aliphatic carboxylic acids having 1 to 4 carbon atoms, such as N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and
  • N-vinyl lactams having 5 to 7 ring atoms for. N-vinylpyrrolidone, N-vinylpiperidone,
  • N-vinylmorpholinone and N-vinylcaprolactam monoethylenically unsaturated monomers bearing urea groups, such as
  • N-vinyl and N-allyl urea as well as derivatives of imidazolidin-2-one, e.g. B.
  • Examples of basic monomers Mb include
  • Vinyl-substituted nitrogen heteroaromatics such as 2-, 3- and 4-vinylpyridine, N-vinylimidazole; and monoethylenically unsaturated monomers having a primary, secondary or tertiary amino group, in particular monomers of the general formula I
  • X is oxygen or a group NR 4a ;
  • A is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2 or 1, 3-propanediyl,
  • 1,4-butanediyl or 2-methyl-1,2-propanediyl optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms as in 3-oxapentane-1, 5-diyl;
  • R 1a , R 1b independently of one another represent hydrogen, C 1 -C 10 -alkyl, C 1 -C 10 -cycloalkyl, phenyl or phenyl-C 1 -C 4 -alkyl and in particular both each represent C 1 -C 4 -alkyl;
  • R 2a is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl;
  • R 3a is hydrogen or C 1 -C 4 -alkyl and in particular hydrogen; and R 4a is hydrogen or C 1 -C 4 -alkyl and in particular hydrogen.
  • Examples of monomers of the formula I are 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylamide, 3- (N, N-dimethylamino) propyl acrylate , 3- (N, N-Dimethylamino) propyl methacrylate, 3- (N, N-dimethylamino) propylacrylamide, 3- (N, N-dimethylamino) propylmethacrylamide and 2- (N, N-dimethylamino) ethylmethacrylamide, whereby 3- (N, N) , N-dimethylamino) propyl methacrylate is particularly preferred.
  • the monomers Mb furthermore include anionic or acidic monoethylenically unsaturated monomers.
  • anionic or acidic monoethylenically unsaturated monomers examples for this are: monoethylenically unsaturated monomers which have a sulfonic acid group, and the salts of such monomers, in particular the alkali metal salts, for. As the sodium or potassium salts and ammonium salts.
  • Preferred acidic monomers Mb are the abovementioned monoethylenically unsaturated monomers having one or two carboxyl groups.
  • the polymers P2 are linear or branched poly-C 2 -C 4 -alkylene ethers, ie polymers which essentially, i. H. at least 90% by weight, based on the weight of the polymers P2, of repeating units of the formula II
  • A is a C2-C4 alkylene group such as ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl or butane-1, 3 -diyl stands.
  • Preferred among the polymers P2 are those which contain at least 50% by weight, advantageously at least 70% by weight, in particular at least 80% by weight and especially at least 90% by weight of ethylene oxide unit, ie. are constructed of groups of formula II wherein A is 1, 2-ethanediyl.
  • the aliphatic polyethers may have structural units derived from C3-C4 alkylene oxides.
  • Particularly preferred polyethers P2 are those of the general formula III
  • R a is hydrogen, C 1 -C 20 -alkyl or benzyl
  • X is oxygen or NH
  • R b is hydrogen or methyl, where at least 50 mol%, in particular at least 70 mol% and preferably at least 90 mol% of the Groups R b are hydrogen
  • p represents an integer whose mean value is in the range of 10 to 500, preferably 20 to 250 and especially 25 to 100 (number average).
  • Suitable polyethers P2 are known to the person skilled in the art and for the most part are commercially available, for example under the trade names Pluriol® and Pluronic® (polyethers from BASF Aktiengesellschaft).
  • the polyether chains P1 and P2 can be used directly with each other, i. H. be linked via a chemical bond, or via a spacer, the latter being preferred. In general, then the polymer chains P1 and P2 are linked to each other via functional groups with the spacer, z. B. via ester, amide, urea, thiourea or urethane groups.
  • Suitable spacers are, in particular, polyvalent aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon radicals having generally 2 to 20 carbon atoms, which are linked to the polymer chains P1 and P2 via the abovementioned functional groups.
  • the spacer has on average, at least 1, 5, in particular at least 2, z. B. 1, 5 to 6, in particular 2 to 4 valences, so that the block copolymers on average at least 1, 5, in particular at least 2, z. B.1, 5 to 6, in particular 2 to 4 polymer chains P1 or P2.
  • the polymer chains P1 and P2 are each linked via a urethane group or urea group with a spacer.
  • Such block copolymers are obtainable by reacting the OH or NH 2 -functionalized polymers polymers P1 and P2 successively or simultaneously with a polyisocyanate compound V, which preferably has a functionality with respect to the isocyanate groups of at least 1.5, in particular 1.5 to 6 and especially 2 to 4.
  • polyisocyanate compounds V are aliphatic, cycloaliphatic and aromatic di- and polyisocyanates and the isocyanurates, allophanates, urethdiones and biurets of aliphatic, cycloaliphatic and aromatic diisocyanates.
  • the compounds V have on average from 2 to 4 isocyanate groups per molecule.
  • suitable compounds V are aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanates, commercially available mixtures of toluene-2,4- and 2,6-diisocyanate (TDI), m-phenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, cumene 2,4-diisocyanate, 1, 5-naphthalene diisocyanate, p-xylylene diisocyanate, p-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate,
  • diisocyanates preference is given to those whose isocyanate groups differ in their reactivity, such as toluene-2,4-diisocyanate, IPDI, mixtures thereof and cis- and trans-isophorone diisocyanate.
  • a biuret or an isocyanurate of an aliphatic or cycloaliphatic diisocyanate compound is used for the preparation of the block copolymers, for example the cyanurate of tetramethylene diisocyanate or of hexamethylene diisocyanate.
  • compositions to be stabilized may also contain other conventional surface-active substances.
  • Particularly suitable are anionic surface-active substances, for. B. those of groups b18) to b24), in particular the groups b18), b19), b22) and b23) and nonionic emulsifiers, in particular nonionic emulsifiers having at least one poly-C2-C4-alkylene ether and anionic emulsifiers, in particular nonionic Emulsifiers of groups b1), b2), b4), b9), b10) and b17), as well as copolymers of group b3).
  • emulsifiers typically have a molecular weight of not more than 2000 daltons and in particular not more than 1000 daltons.
  • the anionic emulsifiers include the substances mentioned in groups b18) to b24), in particular the abovementioned carboxylates, in particular alkali, alkaline earth and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g.
  • Nonionic surfactants with poly-C 2 -C 4 -alkylene ether groups include in particular:
  • Substances of group b1) such as fatty alcohol C2-C3 alkoxylates and oxo alcohol C2-C3 alkoxylates, in particular ethoxylates and ethoxylate co-propoxylates with Al- koxil mecanical z.
  • alkoxylates in particular ethoxylates and propoxylates of Cs-Cso-alkanols or alk (adi) enols, z.
  • iso-tridecyl alcohol lauryl alcohol, oleyl alcohol or stearyl alcohol, and their C 1 -C 4 -alkyl ethers and C 1 -C 4 -alkyl esters e.g. their actions;
  • Substances of group b2) in particular ethylene oxide-propylene oxide block copolymers;
  • Substances of group b3) such as alkoxylated, in particular ethoxylated and / or propoxylated animal and / or vegetable fats and / or oils, for example
  • Corn oil ethoxylates such as alkylphenol C 2 -C 3 -alkoxylates, in particular alkylphenol ethoxylates and alkylphenol ethoxylate-co-propoxylates, such as ethoxylated isooctyl, octyl or nonylphenol, tributylphenol polyoxyethylene ethers,
  • Substances of groups b4) and b9) such as fatty amine C 2 -C 3 -alkoxylates, in particular fatty amine ethoxylates and fatty amine ethoxylate-co-propoxylates, and also fatty acid diethanolamidoalkoxylates, in particular their ethoxylates, substances of group b 10), sugar surfactants with poly-C 2 -C 3 -alkylene ether groups, e.g. B. Polyoxyethylensorbitanfettklader, ethoxylated alkylpolyglycosides and ethoxylated N-alkylgluconamides.
  • compositions to be stabilized according to the invention generally comprise at least one surface-active substance in an amount of 0.05 to 20 parts by weight, frequently 0.1 to 10 parts by weight, in particular 0.2 to 8 parts by weight and especially 0.5 to 5 parts by weight, based on 1 part by weight of the active substance to be stabilized.
  • the total concentration of the surfactant (s) is typically in the range of 1 to 50 wt%, more preferably in the range of 1 to 45 wt%, and especially in the range of 1 to 40 wt%, based on the total weight of the aqueous composition.
  • the compositions to be stabilized according to the invention contain at least one solubilizing polymer, in particular one of the abovementioned block copolymers and optionally one or more conventional surface-active substances, in particular a nonionic surface-active substance.
  • the proportion of the solubilizing polymers, in particular of the abovementioned block copolymers, in the total amount of the surface-active substance (s) contained in the composition is typically at least 50% by weight, in particular at least 80% by weight.
  • compositions to be stabilized according to the invention comprise at least one conventional surfactant, in particular a conventional nonionic surfactant having a poly-C 2 -C 4 -alkylene oxide group, in particular at least one nonionic surfactant, which is among those described in the groups b1), b2), b3), b4), b9), b10) and b17) and especially among the substances mentioned in groups b1), b2) and b17), and optionally one or several conventional anionic surface-active substances, in particular at least one of the groups b18), b22) and b23 mentioned substances.
  • a conventional nonionic surfactant having a poly-C 2 -C 4 -alkylene oxide group in particular at least one nonionic surfactant, which is among those described in the groups b1), b2), b3), b4), b9), b10) and b17) and especially among the substances mentioned in groups b1), b2) and b17), and optionally
  • the proportion of the at least one nonionic surface-active substance in the total amount of the surface-active substance (s) contained in the composition is typically at least 20% by weight, in particular at least 30% by weight.
  • the weight ratio of conventional surface-active substances to active substance in this embodiment is typically in the range from 1:20 to 20: 1, in particular in the range from 1:10 to 10: 1.
  • the active substances are active substances for crop protection, in particular insecticidal and / or fungicidal active substances.
  • the compositions to be stabilized according to the invention comprise at least one active ingredient which tends to crystallize.
  • the homo- and copolymers used according to the invention lead to a significantly reduced crystallization tendency of the active ingredient.
  • fungicidal active compounds that can be formulated using the homo- or copolymers P according to the invention include the following organic compounds:
  • strobilurins e.g. Azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, cresoxymethyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, oryssastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) - carbamic acid methyl ester, (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] - benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethyl) phenyl) -3-methoxy-acrylic acid methyl ester;
  • Carboxylic acid amides • Carboxylic acid anilides, such as. Benalaxyl, Benodanil, Bixafen, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Metalaxyl, ofuracene, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamide, Tiadinil, 4-difluoromethyl-2-methyl-thiazole 5-Carboxylic acid (4'-bromo-biphenyl-2-yl) -amide, 4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid- (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4- difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluoro-biphenyl-
  • Carboxylic acid morpholides such as. Eg dimethomorph, flumorph
  • Benzoic acid amides such as. Flumetover, fluopicolide (picobenzamide), zoxamide;
  • carboxylic acid amides such as. Carpropamide, diclocymet, mandipropamide, ethaboxam, penthiopyrad, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) - 2-methanesulfonylamino-3-methyl-butyramide, N- (2- [4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethane sulfonylamino-3-methyl-butyramide;
  • Triazoles such as. B. bitertanol, bromuconazoles, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, flutinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, Tetraconazole, triadimenol, triadimefon, triticonazole;
  • imidazoles such as Cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;
  • Benzimidazoles such as. Benomyl, carbendazim, fuberidazole, thiabendazoles; and others, such as ethaboxam, etridiazoles, hymexazoles;
  • Nitrogen-containing heterocyclyl compounds e.g. B. • pyridines, such as Fluazinam, pyrifenox, 3- [5- (4-chloro-phenyl) -2,3-dimethylisoxazolidin-3-yl] -pyidine;
  • Pyrimidines such as. Bupirimate, Cyprodinil, Ferimzone, Fenarimol, Mepanipyrim, Nuarimol, Pyrimethanil; • piperazines, such as triforine;
  • Pyrroles such as fludioxonil, fenpiclonil
  • Morpholines such as aldimorph, dodemorph, fenpropimorph, tridemorph
  • Dicarboximides such as iprodione, procymidone, vinclozolin;
  • Dithiocarbamates such as Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram; Carbamates, such as diethofencarb, benthiavalicarb, iprovalicarb, propamocarb,
  • Guanidines such as dodine, iminoctadine, guazatine
  • Antibiotics such as kasugamycin, polyoxins, streptomycin, validamycin A;
  • Organometallic compounds such as fentin salts
  • Sulfur-containing heterocyclyl compounds such as isoprothiolanes, dithianone;
  • Organophosphorus compounds such as edifenphos, fosetyl, fosetylaluminum,
  • Organochlorine compounds such as thiophanate methyl, chlorothalonil, dichlofluanid, tolylfluanid, flusulphamides, phthalides, hexachlorobenzene, pencycuron, quintocene; Nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton;
  • herbicidal active substances that can be formulated using the homo- or copolymers P of the invention include:
  • 1, 3,4-thiadiazoles such as buthidazole and cyprazole
  • Amides such as allidochlor, benzoylpropyl, bromobutide, chlorthiamide, dimepiperate, dimethenamid, diphenamid, etobenzanide, flampropmethyl, fosamine, isoxaben, metazachlor, monalides, naptalame, pronamide, propanil;
  • Aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate, sulfosates;
  • Aminotriazoles such as amitrole, anilides such as anilofos, mefenacet;
  • Anilides such as anilofos, mefenacet
  • Aryloxyalkanoic acid such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilides, triclopyr;
  • Benzoic acids such as Chloramben, Dicamba;
  • Benzothiadiazinones such as bentazone
  • Bleachers such as Clomazone, Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazolate, Sulcotrione; Carbamates such as carbetamide, chlorobufam, chlorpropham, desmedipham,
  • dihydrobenzofurans such as ethofumesates
  • dihydrofuran-3-one such as flurtamone
  • Dinitroanilines such as Benefin, Butraline, Dinitramine, Ethalfluralin, Fluchloralin, Isopropaline, Nitralin, Oryzalin, Pendimethalin, Prodiamine, Profluralin, Trifluralin,
  • Dinitrophenols such as bromofenoxime, dinoseb, dinoseb acetate, dinoterb, DNOC, medinoterb acetate; Diphenyl ethers such as acifluorfen-sodium, aclonifen, bifenox, chloronitrofen,
  • Dipyridyls such as cyperquat, difenzoquatmethylsulfate, diquat, paraquatdichloride;
  • Imidazoles such as isocarbamide; Imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazamethabenzomethyl, imazethapyr, imazapic, imazamox;
  • Oxadiazoles such as methazoles, oxadiargyl, oxadiazon;
  • Phenols such as bromoxynil, loxynil; Phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofop-butyl, diclofopmethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl , Isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl; Phenylacetic acids such as chlorfenac;
  • phenylpropionic acids such as chlorophenprop-methyl
  • Ppi agents such as benzofenap, flumiclorac-pentyl, flumioxazine, flumipropyne, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimin;
  • Pyridazines such as Chloridazon, Maleic hydrazide, Norflurazon, Pyridate; Pyridinecarboxylic acids such as clopyralid, dithiopyr, picloram, thiazopyr;
  • Pyrimidyl ethers such as pyrithia-bac acid, pyrithiobac-sodium, KIH-2023, KIH-6127;
  • sulfonamides such as flumetsulam, metosulam
  • Triazole carboxamides such as triazofenamide
  • Uracils such as bromacil, lenacil, terbacil; • Benazoline, Benfuresate, Bensulide, Benzofluor, Bentazone, Butamifos,
  • Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, Rimsul - furon, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron; Cytogenetic agents of the cyclohexenone type, such as alloxydim, clethodim,
  • cyclohexenone-type herbicidal active compounds are: tepraloxydim (compare AGROW, No. 243, 3.1.195, page 21, caloxydim) and 2- (1- [2- ⁇ 4-chlorophenoxy ⁇ propyl-oxyimino] butyl) - 3-hydroxy-5- (2H-tetrahydrothio-pyran-3-yl) -2-cyclohexen-1-one and of the sulfonylurea type: N - (((4-methoxy-
  • insecticides which can be formulated using the homo- or copolymers P according to the invention include:
  • Organo (thio) phosphates such as acephates, azamethiphos, azinphos-ethyl, azinphos-methyl, cadudsafos, chloroethoxyphos, chlorfenvinphos, chloremephos, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, coumaphos, cyanophos, demeton-S-methyl, diazinon , Dichlorvos / DDVP, dicrotophos, dimethoates, dimethylvinphos, disulphoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, isoxathione, malathion, mecarbam, methamidophos, methidathione, methylparathion, mevinphos , Monocrotophos,
  • Phosphamidone Phosphamidone, phorates, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthione, quinalphos, sulfo tep, Sulprophos, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiotom, Triazophos, Trichlorfon, Vamidothion;
  • Carbamates such as alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, ethofoncarb, fenobucarb, fenoxycarb, formethanate, furathiocarb, isoprocarb, methiocarb, methomyl,
  • Pyrethroids such as acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma
  • Arthropod growth regulators a) chitin synthesis inhibitors z.
  • B. benzoylureas such as bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenonoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron,
  • Nicotinic receptor agonists / antagonists acetamipride, clothianidin, difitanofuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, nicotine, benzaput, cartap hydrochloride, thiocyclam, sodium thiosultap and AKD1022;
  • GABA antagonists such as acetoprol, chlordane, endosulfan, ethiprole, gamma-HCH (lindane), fipronil, vaniliprole, pyrafluprol, pyriprole, vaniliprole, phenylpyrazole compounds of the formula I- 1
  • Macrocyclic lactones such as abamectin, emamectin, emamectin benzoates, miimectectin, lepimectin, spinosad; • METI I compounds such as Fenazaquin, Fenpyroximate, Flufenerim, Pyridaben, Pyrimidifen, Rotenone, Tebufenpyrad, Tolfenpyrad;
  • METI II and III compounds such as acequinocyl, fluacryprim, hydramethylnone;
  • decoupling compounds such as Chlorfenapyr, DNOC
  • inhibitors of oxidative phosphorylation such as azocyclotine, cyhexatin, di-thiuron, fenbutatin oxide, propargite, tetradifone;
  • synergists such as piperonyl butoxide and Tribufos
  • Sodium Channel Blockers such as Indoxacarb, Metaflumizone
  • Mite growth inhibitors clofentezine, hexythiazox, etoxazole;
  • Chitin synthesis inhibitors such as buprofezin, bistrifluron, chlorofluorazuron, diflubenuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,
  • Lipid biosynthesis inhibitors such as spirodiclofen, spiromesifen, spirotetramate
  • octapaminergic agonists such as amitraz
  • modulators of the ryanodine receptor such as flubendiamide; Various: Amidoflumet, Benclothiaz, Benzoximate, Bifenazate, Bromoproparate, Cyenopyrafen, Cyflumetofen, Chinomethionate, Dicofol, Fluoroacetate, Pyralidyl, Pyrifluquinazone, N-R'-2,2-Dihalo-1-R "-cyclopropanecarboxamide 2- ( 2,6-dichloro- ⁇ , ⁇ , ⁇ -trifluoro-p-tolyl) hydrazone, N-R'-2,2-di (R '") propionamide 2- (2,6-dichloro- ⁇ , ⁇ , ⁇ -trifluoro-p-tolyl) -hydrazone, wherein R 'is methyl or ethyl, Halo is chlorine or bromine, R "is hydrogen or methyl and
  • R '" is methyl or ethyl
  • Anthranilamides such as chloranthraniliprole, and the compound of formula I ⁇ 2
  • R is methyl or ethyl and Het * for 3,3-dimethylpyrrolidin-1-yl, 3-methylpiperidin-1-yl, 3,5-dimethylpiperidin-1-yl, 4-methylpiperidin-1-yl, hexa-hydroazepine 1-yl, 2,6-dimethylhexahydroazepin-1-yl or 2,6-dimethylmorpholin-4-yl.
  • a preferred embodiment of the invention relates to the use of the homo- or copolymers P according to the invention for the preparation of Wirkstoffformulierun- conditions of water-insoluble or poorly soluble fungicides or the use of the homo- or copolymers of the invention P for solubilization of water-insoluble or poorly soluble fungicides in an aqueous medium.
  • the active ingredient is selected from
  • Strobilurins e.g. Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin, in particular pyraclostrobin, conazole fungicides, in particular prochloraz, cyproconazole, epoxiconazole, fluconconazole, hexaconazole, metconazole, penconazole, propiconazole, prothioconazole, Tebuconazole and triticonazole and especially epoxiconazole, metconazole, fluconazole or prothioconazole,
  • 6-Aryl- [1,2,4] triazolo [1,5-a] -pyrimidines e.g.
  • 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine e.g.
  • 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine e.g.
  • 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine e.g.
  • the active substance formulations according to the invention comprise a combination of at least two active substances, in particular at least two fungicides.
  • the active ingredient combination is a combination of at least one conazole fungicide, especially epoxiconazole or metconazole, with at least one strobilurin, in particular pyraclostrobin, and optionally a further active ingredient, eg.
  • Fenpropidin a combination of at least one conazole fungicide, especially epoxiconazole or metconazole, with at least one carboxylic acid amide, in particular a carboxylic acid anilide, especially boscalid, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-bromo-biphenyl-2-yl ) amide,
  • Fenpropidin a combination of two different conazole fungicides, especially epoxiconazole, with at least one other conazole fungicide other than epoxiconazole, in particular a conazole fungicide comprising prochloraz, cyproconazole, fluquinconazole, hexaconazole, metconazole, penconazole, propiconazole, prothioconazole, tebuconazole and triticonazole, and especially Metconazole, fluquinconazole and prothioconazole is selected; and a combination of at least one 6-aryl- [1,2,4] triazolo [1,5-a] pyrimidine, especially 5-chloro
  • a further preferred embodiment of the invention relates to the use of the homopolymers and copolymers P according to the invention for stabilizing aqueous compositions containing at least one insecticidal active ingredient which is in particular selected from arylpyrroles such as chlorfenapyr, pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfenvalerates, Etofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin and permethrin, neonicotinoids and semicarbazones such as metaflumizone.
  • a preferred embodiment of the invention also relates to the use of the homopolymers and copolymers P for stabilizing insecticides, in particular arylpyrroles, of pyrethroids, of neonicotinoids and of metaflumizone, in the aqueous phase.
  • the homopolymers and copolymers P according to the invention are suitable for stabilizing active pharmaceutical ingredients in aqueous active ingredient compositions.
  • active pharmaceutical ingredients are benzodiazepines, antihypertensives, vitamins, cytostatics - in particular taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antimycotics, chemotherapeutics, urologics , Platelet aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, serums, thyroid therapeutics, psychotropic drugs, Parkinson's and other antihyperkinetics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering drugs, liver therapeutics, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport
  • the invention also relates to active ingredient compositions, in particular active compound formulations, which contain at least one active substance which is sparingly soluble in water, at least one surface-active substance and at least one homopolymer or copolymer P.
  • active ingredient compositions in particular active compound formulations, which contain at least one active substance which is sparingly soluble in water, at least one surface-active substance and at least one homopolymer or copolymer P.
  • the compositions may be formulations, ie compositions containing the active ingredient in concentrated form, or aqueous ready-to-use compositions containing the active ingredient in a diluted form.
  • formulations according to the invention which contain at least one homopolymer or copolymer P are: aqueous formulations in which the active ingredient is in suspended or dispersed form (so-called SC formulations); water-dilutable emulsifiable concentrates (so-called EC formulations) in which the active ingredient is dissolved in a water-immiscible solvent, for example a hydrocarbon or a vegetable oil or vegetable oil derivative such as a vegetable oil methyl ester; water-dilutable oil suspension concentrates (so-called OD formulations) in which the active ingredient is dispersed in a water-immiscible solvent such as a hydrocarbon or vegetable oil or vegetable oil derivative such as a vegetable oil methyl ester; water-dilutable concentrates in which the active ingredient is dissolved in a water-miscible solvent, for example a lactam such as N-methylpyrrolidone or N-ethylpyrrolidone, a lactone such as butyrolact
  • TLC formulations Tetrahydrofuran or dioxane, an alkanol or alkanediol such as ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol or butanediol or dissolved in a mixture of the aforementioned water-miscible solvent is present (so-called TLC formulations).
  • a water-miscible solvent is understood as meaning an organic solvent which completely dissolves in water at 25 ° C. to at least 100 g / l and in particular has no miscibility gap with water at this temperature; solid formulations such as powders or granules which are dilutable with water and which typically contain a solid carrier.
  • the total concentration of active ingredient (s) is typically in the range from 0.1 to 80% by weight, frequently in the range from 0.5 to 70% by weight, in particular in the range from 0.5 to 60% by weight % and especially in the range of 1 to 50 wt.% or 1 to 40 wt.% or 2 to 30 wt.%, based on the total weight of the formulation.
  • the concentration of surface-active substances in the formulations is typically in the range from 1 to 50% by weight, in particular in the range from 1 to 45% by weight and especially in the range from 1 to 40% by weight, based on the total weight of the drug formulation.
  • the active ingredient formulations of the invention contain the at least one homo- or copolymers P usually in an amount of at least 1 wt .-%, preferably at least 5 wt .-%, z. B. in an amount of 5 to 2000 wt .-%, often 10 to 1000 wt .-%, in particular 10 to 500 wt .-% or 10 to 300 wt .-% or 10 bis 100 wt .-%, especially in an amount of 10 to 60 wt .-%, based on the or the active ingredient (s).
  • the concentration of the homopolymers or copolymers P is typically in the range from 0.01 to 15% by weight, in particular in the range from 0.1 to 10% by weight and especially in the range from 0.5 to 6 Wt .-%, based on the total weight of the formulation.
  • Preferred formulations are aqueous formulations.
  • the total concentration of drug (s) is typically in the range of 0.1 to 80 wt%, often in the range of 0.5 to 70 wt%, more preferably in the range of 0.5 to 60 wt%. % and especially in the range of 1 to 50% by weight, or in the range of 1 to 40% by weight or 2 to 30% by weight, based on the total weight of the aqueous composition.
  • the concentration of surface-active substances in the aqueous formulations is typically in the range from 1 to 50% by weight, in particular in the range from 1 to 45% by weight and especially in the range from 1 to 40% by weight, based on the total weight the drug formulation.
  • the concentration of the homopolymers or copolymers P is typically in the range from 0.01 to 15% by weight, in particular in the range from 0.1 to 10% by weight and especially in the range from 0.5 to 6 wt .-%, based on the total weight of the formulation.
  • the aqueous drug composition contains water as a diluent.
  • the composition may also contain one or more organic, water-miscible solvents. The proportion of solvents will generally not overwrite 10% by weight, based on the weight of the composition.
  • the water or mixture of water with the water-miscible organic solvent forms a continuous phase containing the active ingredient as a disperse phase.
  • the active substance or effect substance and the surface-active substance are presumably in the form of aggregates (eg micelles) of active substance and surface-active substance.
  • This active substance-containing phase thus forms a disperse phase which contains the active substance or the effect substance and the surface-active substance.
  • the homopolymers and copolymers P according to the invention stabilize this disperse phase and effectively prevent a separation of the active substance, as can occur, for example, by crystallization of the active ingredient.
  • the active ingredient is poorly soluble in water, it is in suspended form.
  • the mean particle size of the active ingredient particles is typically in the range from 10 nm to 5 ⁇ m, frequently in the range from 20 nm to 3 ⁇ m and in particular in the range from 100 nm to 2 ⁇ m.
  • the dgo value ie the diameter which falls below more than 90% by volume of the particles, does not exceed a value of 10 ⁇ m, in particular 5 ⁇ m.
  • the invention also relates to aqueous active ingredient preparations which contain the active ingredient in dilute form.
  • These drug preparations are obtainable by diluting a drug formulation with water, wherein the dilution is carried out according to the invention in the presence of the homo- or copolymer P.
  • the homo- or copolymer may be partially or completely contained in the formulation intended for dilution or it may be added during dilution with water.
  • the formulation to be diluted contains the at least one homo- or copolymer P.
  • the water used for dilution contains the at least one homo- or copolymer.
  • the active ingredient preparation obtainable by dilution with water contains, in addition to the active substance and the at least one surface-active substance, also the at least one homo- or copolymer P.
  • the homo- or copolymer P is generally employed in an amount of 0.05 to 20 parts by weight, preferably in an amount of 0.1 to 10 parts by weight, based on 1 part by weight of the active ingredient.
  • the active ingredient preparations obtainable by dilution with water contain the polymer P in an amount of from 0.01 to 5% by weight, in particular from 0.1 to 3% by weight, based on the total weight of the active ingredient preparation.
  • the amount of water used for dilution is determined in a manner known per se according to the desired concentration of the active ingredient for the application.
  • at least 10 parts by volume often at least 20 parts by volume, more preferably at least 50 parts by volume, e.g. B. 10 to 10,000 parts by volume, in particular 20 to 5000 parts by volume and especially 50 to 4000 parts by volume of water or an aqueous solution of the polymer P, based on 1 part by volume of the formulation.
  • the average particle size of the active ingredient particles typically in the range of 10 nm to 5 microns, often in the range of 50 nm to 3 microns and in particular in the range of 100 nm to 2 microns.
  • the dgo value ie the diameter which falls below more than 90% by volume of the particles, does not exceed a value of 10 ⁇ m, in particular 5 ⁇ m.
  • the aqueous active ingredient composition When diluted with water, the aqueous active ingredient composition, if it contains a solubilizing polymer, provides a dilute aqueous composition in which the active ingredient is dispersed in an extremely fine, i.e. H. nanodisperse distribution in the aqueous phase.
  • the active substance composition comprises a solubilizing polymer, in particular one of the abovementioned block copolymers, the average particle size of the active substance particles is clearly below 1000 nm and in many cases no longer 500 nm, often not more than 400 nm, in particular not more than 300 nm. more preferably not more than 250 nm, and more preferably not more than 200 nm, and is e.g.
  • the aggregates may also become so small that they are no longer in the form of detectable, discrete particles (particle size ⁇ 20 nm, ⁇ 10 nm or ⁇ 5 nm).
  • the stabilizing effect also occurs in aqueous dilutions in which the mean particle size (volume average) is above 1000 nm, z. B. in the range of 1 micron to 5 microns, often in the range of 1 to 3 microns and in particular in the range of 1 to 2 microns.
  • the active ingredient compositions may contain customary formulation auxiliaries in the quantities customary for this purpose. These include, for example, agents for modifying the rheology (thickener), antifoaming agents, bactericides, antifreeze agents for controlling the pH, and the like.
  • Suitable thickeners are compounds which give pseudoplastic flow behavior to aqueous compositions, ie high viscosity at rest and low viscosity in the agitated state.
  • polysaccharides are, for example, such as xanthan gum (Kelzan ® from Kelco; or Veegum ® from RT Vanderbilt. Rhodopol ® 23 from Rhone Poulenc.)
  • xanthan gum Kelzan ® from Kelco; or Veegum ® from RT Vanderbilt.
  • Rhodopol ® 23 from Rhone Poulenc.
  • suitable antifoam agent for example, silicone emulsions (such. As silicone ® SRE, from Wacker, or Rhodorsil ® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides may be added to stabilize the compositions of the invention against attack by microorganisms. These are typically isothiazolinone or isothiazolone compounds, eg. B. 1, 2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazol-3-one, 2-methylisothiazol-3-one or 2-octylisothiazol-3-one, for example, under the trade names Prixel ® the Fa. Arch Chemical Inc., Acetide ® RS from. Thor Chemie and Kathon ® MK from Rohm & Haas are available.
  • Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are used in aqueous formulations, usually in amounts of not more than 20 wt .-%, z. B. 1 to 20 wt .-% and in particular 2 to 10 wt .-%, based on the total weight of the aqueous active ingredient formulation.
  • the active compound formulations of the invention may contain from 1 to 5% by weight, based on the total amount of the prepared preparation, of pH control of the preparation or of the diluted administration form, the amount and type of the agent used being determined by the chemical properties and Amount of the active ingredients and the homo- or copolymer P directed.
  • means for pH regulation are alkali metal salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • aqueous active compound compositions according to the invention can be carried out in a manner known per se and depends in a manner known per se on the type of formulation. Methods for this are known, for example from US 3,060,084, EP-A 707445, Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-148, Perry's Chemical Engineers Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp.
  • the aqueous active substance compositions according to the invention are prepared by suspending at least one surface-active substance, at least one active ingredient and optionally a part or all of the customary auxiliaries and optionally the homo- or copolymer in water and then crushed by a grinding process, the active ingredient to the desired particle size.
  • Suspension can then be the residual amounts of auxiliaries, if desired, and the remainder of homo- or copolymer P, if not already added before grinding incorporate.
  • at least a subset of the homo- or copolymers preferably at least 50 wt .-% of the provided in the formulation amount of polymer P already added before grinding.
  • Suitable devices for grinding are ball mills, colloid mills and bead mills, wherein one or more grinding operations are usually carried out until the desired degree of division is achieved.
  • the preparation of the aqueous active compound compositions according to the invention is carried out by initially introducing at least one surface-active substance, in particular a block copolymer, and the active substance (s) in an organic solvent in which they are soluble.
  • the solvent is suitably chosen so that it has a boiling point of ⁇ 100 0 C.
  • the solution is mixed with water and the mixture is heated until the organic solvent is substantially evaporated.
  • water is added to the mixture during heating to replace coevaporated water.
  • the aqueous active ingredient dispersion is added to this finally with the homo- or copolymer P.
  • the polymer is suitably added in the form of an aqueous solution.
  • the homogeneous mixture in the form of a solution of the ingredients in an organic solvent in water and then substantially or completely remove the organic solvent, for. B. by distillation, which one will compensate for any losses of water in the rule.
  • Suitable solvents for this purpose are in principle those which are capable of dissolving both the active ingredient and the homo- or copolymer P, for example aliphatic nitriles such as acetonitrile and propionitrile, N, N-dialkylamides of aliphatic carboxylic acids such as dimethylformamide and dimethylacetamide, lactams and N-alkyllactams such as N-methylpyrrolidone, N-ethylpyrrolidone or caprolactam, lactones such as gamma-butyrolactone, carbonates such as diethyl carbonate, ethylene carbonate, propylene carbonate, C 1 -C 5 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert.
  • aliphatic nitriles such as acetonitrile and propionitrile
  • Butanol, aliphatic and alicyclic ethers for example tetrahydrofuran or dioxane, halogenated hydrocarbons such as dichloromethane, dichloroethane, esters of aliphatic C 1 -C 4 -carboxylic acids with C 1 -C 6 -alkanols such as ethyl acetate, butyl acetate, butyl formate, methyl propionate, methylbutyrate and mixtures of the abovementioned solvents.
  • Preferred organic solvents are in particular those which have at least a limited miscibility with water, for.
  • Ci-Cs-alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, aliphatic Nitriles such as acetonitrile and propionitrile, N, N-dialkylamides of aliphatic carboxylic acids such as dimethylformamide and dimethylacetamide, N-alkyl lactams such as N-methylpyrrolidone.
  • desired additives and auxiliaries can be incorporated into the composition in a manner known per se.
  • aqueous active compound compositions it is alternatively possible to carry out a solution of the active ingredient in an organic solvent which contains part or all of the surface-active substance and optionally a part or all of the homo- or co-polymer P Water or an aqueous solution which optionally contains a residual amount of surface-active substance and optionally a part or the total amount of the homo- or copolymer P, and then the organic solvent is removed.
  • the mixing can be carried out in suitable stirred vessels, it being possible to submit both water or the aqueous solution of the homo- or copolymer P and for this purpose gives the solution of the active ingredient, or alternatively presents the solution of the active ingredient and for this purpose the water or the aqueous solution of homo - or copolymer P gives. Subsequently, the organic solvent is removed completely or partially, for. B. by distillation, optionally adding water.
  • the active substance solution and the water or the aqueous solution of the homopolymer or copolymer P are continuously introduced into a mixing zone and continuously remove the mixture, from which the solvent is then wholly or partly removed.
  • the mixing zone can be configured as desired. Basically, all apparatuses are suitable for this, which allow a continuous mixing of liquid streams. Such apparatuses are known, for. From Continuous Mixing of Fluids (J.H.Henzler) in Ullmann's Encyclopaedia 5th ed. On CD-Rom, Wiley-VCH and also WO 2008/031780 and the literature cited therein.
  • the mixing zones may be configured as static or dynamic mixers or mixed forms thereof.
  • Y mixers, jet mixers or comparable mixers with nozzles are also suitable as mixing zones.
  • the mixing zone is the apparatus described in the "Handbook of Industrial Crystallization” (A. S. Myerson, 1993 Butterworth-Heinemann, page 139, ISBN 0-7506-9155-7) or a comparable apparatus.
  • solid formulations can be prepared, for example, by mixing the active substance, the at least one surface-active substance and the at least one homo- or copolymer P, if appropriate together with a solid carrier and, if appropriate, further excipients and mixing them in a suitable manner, eg. B. milled by means of an air jet mill to the desired fineness.
  • a suitable manner eg. B. milled by means of an air jet mill to the desired fineness.
  • the homo- or copolymers P generally result in an improvement in the stability of aqueous suspensions of poorly water-soluble active ingredients without the need for a conventional surface-active substance, but preferably such a surface-active substance is present is.
  • the homopolymers or copolymers P according to the invention act as dispersing aids or as protective colloid.
  • a further subject of the invention relates to the use of the homo- or copolymers P for the dispersion of poorly water-soluble organic active ingredients in aqueous compositions.
  • the homo- or copolymer P is generally used in an amount of 0.05 to 20 parts by weight, preferably in an amount of 0.1 to 10 parts by weight, in particular 0.2 to 5 parts by weight, based on 1 part by weight of in the aqueous phase to be dispersed active ingredient.
  • aqueous suspensions of active substance can be prepared with or without additional surface-active substance.
  • the active ingredient concentration in these suspensions is typically in the range of 0.1 to 60 wt .-%, often in the range of 1 to 60 wt .-%, in particular in the range of 2 to 50 wt .-%, especially 3 to 40 wt. -% or 5 to 30 wt .-%, based on the total weight of the dispersion.
  • the active ingredient compositions according to the invention can be used in a manner comparable to conventional formulations of the particular active or effect substance.
  • drug formulations containing at least one insecticidal, acaricidal or nematicidal agent may be used to control harmful arthropods, e.g. As insects or acarids or nematodes are used.
  • the active ingredient formulations according to the invention contain at least one fungicidal active ingredient, they can be used to combat harmful fungi.
  • the active ingredient formulations according to the invention contain a herbicidal active ingredient, they can be used for combating grass weeds and the like.
  • compositions according to the invention are particularly suitable for protecting plants from infestation with harmful organisms such as insects, acarids, nematodes or for protection against infestation with phytopathogenic Fungi and the like, or used in the seed treatment or in the protection of materials, for example for the protection of lignocellulosic materials such as wood, against infestation with noxious insects, such as wood-destroying beetles, termites, ants and the like, or against an infestation with wood-discoloring or wood-destroying fungi.
  • harmful organisms such as insects, acarids, nematodes or for protection against infestation with phytopathogenic Fungi and the like
  • materials for example for the protection of lignocellulosic materials such as wood, against infestation with noxious insects, such as wood-destroying beetles, termites, ants and the like, or against an infestation with wood-discoloring or wood-destroying fungi.
  • compositions according to the invention can also be used in cosmetics or in medicine.
  • Feed 1 400 g of isopropanol, 75% methyl methacrylate and 225 g of methacrylic acid
  • Feed 2 50 g of isopropanol and 8 g of tert-butyl perpivalate
  • Feed 1 250 g of isopropanol and 225 g of methacrylic acid
  • Feed 2 75 g of methyl acrylate and 100 g of isopropanol
  • Feed 3 100 g of isopropanol and 8 g of tert-butyl perpivalate
  • Feed 1 133 g of isopropanol and 100 g of methacrylic acid
  • Feed 2 16.3 g of isopropanol and 2.7 g of tert-butyl perpivalate feed 3: 1, 0 g of tert-Butylperneodecanoat and 20 g of isopropanol
  • Feed 1 contained 200 g of isopropanol and 60 g of methyl methacrylate.
  • Feed 2 contained 200 g of isopropanol and 240 g of methacrylic acid. This gave a clear, highly viscous solution of the polymer P-6 with a solids content of 23.9 wt .-%.
  • the K value is given in Table 1.
  • the polymerization was carried out analogously to the instructions for preparation example 5 with the following differences:
  • the original contained 200 g of isopropanol, 10.75 g of feed 1 and 24.31 g of feed 2.
  • Feed 1 contained 200 g of isopropanol and 15 g of methyl methacrylate.
  • Feed 2 contained 200 g of isopropanol and 285 g of methacrylic acid. This gave a clear, very viscous aqueous solution of the polymer P-7 with a solids content of 21, 8 wt .-% and a pH of 4.2.
  • the K value is given in Table 1.
  • the polymerization was carried out analogously to the instructions of Preparation Example 5 with the following differences:
  • the original contained 200 g of isopropanol, 13.02 g of feed 1 and 22.06 g of feed 2.
  • Feed 1 contained 200 g of isopropanol, 60 g of methyl methacrylate and O, 3 g of mercaptoethanol.
  • Feed 2 contained 200 g of isopropanol and 240 g of methacrylic acid. This gave a clear, water-containing elastic mass of the polymer P-8 having a solids content of 24.3 wt .-% and a pH of 4.3.
  • the K value is given in Table 1.
  • the polymerization was carried out analogously to the instructions of Preparation Example 5 with the following differences:
  • the original contained 200 g of isopropanol, 13.23 g of feed 1 and 22.06 of feed 2.
  • Feed 1 contained 200 g of isopropanol, 60 g of methyl methacrylate and 4.65 g mercaptoethanol.
  • Feed 2 contained 200 g of isopropanol and 240 g of methacrylic acid. In this way, a clear, viscous aqueous solution having a solids content of 25, 5 wt .-% and a pH of 4.1.
  • the K value is given in Table 1.
  • the polymerization was carried out analogously to the instructions for Preparation Example 5 with the following differences:
  • the original contained 200 g of isopropanol.
  • Feed 1 contained 225 g of methacrylic acid and 400 g of isopropanol.
  • Feed 2 contained 75 g of 2-hydroxypropyl acrylate and 100 g of isopropanol.
  • the K value is given in Table 1.
  • Feed 1 250 g of isopropanol and 225 g of methacrylic acid
  • Feed 2 75 g of N, N-dimethylacrylamide and 100 g of isopropanol
  • Feed 3 100 g of isopropanol and 8 g of tert-butyl perpivalate.
  • Feed 5 20 g of deionized water and 1, 5 g of L (+) - ascorbic acid
  • MAS methacrylic acid
  • AS acrylic acid
  • MMA methyl methacrylate
  • MA methyl acrylate
  • HPA hydroxypropyl acrylate
  • DMAA N, N-dimethylacrylamide
  • VP vinylpyrrolidone
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • Preparation example 18 (block copolymer D2):
  • Feed 2 a consisting of 1817 g of methyl methacrylate, 735 g of styrene and 260 g of methacrylic acid
  • feed 1b consisting of 1445 g of tetrahydrofuran, 18.6 g of azobisisobutyronitrile (AIBN) and 58.4 g of mercaptoethanol, were simultaneously added over the course of 2 hours. and kept the mixture under reflux for 24 hours.
  • AIBN azobisisobutyronitrile
  • the active ingredients were dissolved in tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the polymers P and surfactants were dissolved in water. Subsequently, the active ingredient solution and the polymer solution by means of a Y-mixer, analogously to Example 1 of
  • formulations were prepared which, instead of the polymers P, contained the following surface-active substances in the amounts indicated in Table 3.
  • VP-1 copolymer of 1-vinyl-2-pyrolidone and vinyl acetate in a mass ratio of 6: 4 (Luvitec VA 64 from BASF SE)
  • VP-2 Cremophor® CO40 (PEG-40-hydrogenated castor oil; CAS No. 61788-85-0)
  • aqueous formulations V26a to V31a and 32a to 40a were prepared without incorporation of a block copolymer. This gave aqueous formulations containing the active ingredient in suspended form. Stabilities of the suspensions thus prepared corresponded respectively to the stabilities observed in Examples V26 to V31 and 32 to 40.
  • the active ingredient particles may have amorphous, crystalline or mixed forms of amorphous and crystalline form. Within one month of storage at room temperature no discontinuation of the drug can be observed.
  • Dispersant Ethylene oxide-propylene oxide triblock copolymer
  • Wetting agent Naphthalenesulfonic acid-formaldehyde condensate
  • Antifreeze Propylene glycol
  • Fatty alcohol alkoxylate ethoxylate-co-propoxylate of a Ci2-Ci4-alkanol
  • Example V41 no polymer P was added.
  • Example 43 polymer P-5 was added after milling.
  • Example V44 suspension concentrates with boscalid without polymer P (not according to the invention)
  • the preparation was carried out analogously to the instructions given for Example V41.
  • the resulting suspension concentrate had the following composition:
  • the preparation was carried out analogously to the procedure given for Example 42.
  • the resulting suspension concentrate had the following composition:
  • Example V46 suspension concentrates with boscalid, epoxiconazole and adjuvant without polymer P (not according to the invention)
  • composition The preparation was carried out analogously to the instructions given for Example V41.
  • the resulting suspension concentrate had the following composition: composition
  • Example 47 suspension concentrates with boscalid, epoxiconazole, adjuvant and polymer P
  • the preparation was carried out analogously to the procedure given for Example 42, whereby the fatty alcohol alkoxylate was ground with.
  • the resulting suspension concentrate had the following composition:

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne l'utilisation de certains homo- ou copolymères P pour la stabilisation de substances actives organiques dans des compositions ou formulations aqueuses qui contiennent des substances tensioactives.
EP08774789A 2007-07-06 2008-07-04 Utilisation d'homo- et de copolymeres pour la stabilisation de formulations de substances actives Withdrawn EP2180785A2 (fr)

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EP07111979 2007-07-06
EP08774789A EP2180785A2 (fr) 2007-07-06 2008-07-04 Utilisation d'homo- et de copolymeres pour la stabilisation de formulations de substances actives
PCT/EP2008/058711 WO2009007328A2 (fr) 2007-07-06 2008-07-04 Utilisation d'homo- et de copolymères pour la stabilisation de formulations de substances actives

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AU (1) AU2008274352B2 (fr)
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PE (1) PE20090529A1 (fr)
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CN101730466B (zh) 2015-04-08
WO2009007328A3 (fr) 2009-11-12
KR20100057789A (ko) 2010-06-01
UY31209A1 (es) 2009-01-30
CN101730466A (zh) 2010-06-09
BRPI0813749A2 (pt) 2015-01-06
ECSP109852A (es) 2010-02-26
AU2008274352B2 (en) 2014-01-16
AU2008274352A1 (en) 2009-01-15
CA2691966A1 (fr) 2009-01-15
JP5511659B2 (ja) 2014-06-04
IL202785A0 (en) 2010-06-30
AR067858A1 (es) 2009-10-28
JP2010532332A (ja) 2010-10-07
EA201000089A1 (ru) 2010-06-30
CR11167A (es) 2010-04-21
CL2008001991A1 (es) 2009-09-25
WO2009007328A2 (fr) 2009-01-15
MX2009013810A (es) 2010-01-27
PE20090529A1 (es) 2009-06-04

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